The Prince of Wales is to miss the Chinese state banquet next week, but will hold "one-to-one talks" and spend much of the day with President Xi Jinping.
Details of the Chinese state visit were released ahead of Mr Xi's four day official stay in the UK, which begins on Tuesday October 20.
While Charles will not be at the banquet, the Duke and the Duchess of Cambridge are widely anticipated to be attending the evening affair - the couple's first ever state banquet in the UK - but this is yet to be officially confirmed.
It will only be the third time that Kate has been seen in a tiara - the other being her wedding in 2011 and a diplomatic reception in 2013.
Buckingham Palace revealed that William is to call on the president ahead of the banquet and that both the Duke and Duchess will join Mr Xi at a UK Creative Industries event in London on Wednesday October 21.
William visited Beijing earlier this year and is set to record a speech on illegal wildlife trade on the eve of the visit which will be later broadcast on Chinese television.
Mr Xi will also meet with Jeremy Corbyn at Buckingham Palace ahead of the banquet, when the Labour leader could raise concerns about China's human rights record.
Charles, who is a supporter of the Dalai Lama, has had a difficult relationship with China's leadership in the past, but a royal source stressed that the Prince is heavily involved in this visit and is using the opportunity to have one to one, personal dialogues with Mr Xi, rather than meeting him with a cast of thousands.
The Prince and the Duchess of Cornwall will greet Mr Xi on behalf of the Queen at London's Mandarin Oriental Hotel, accompany him to the ceremonial welcome on Horse Guards Parade and then join the Chinese leader for a lunch at the Palace with the Queen.
Charles and Camilla will also host a tea for Mr Xi and his wife Madame Peng Liyuan at their London home Clarence House.
A Clarence House spokeswoman said: "The Prince of Wales and The Duchess of Cornwall have significant involvement in the State Visit by The President of The People's Republic of China.
"Their Royal Highnesses will greet President Xi and Madame Peng on behalf of The Queen, at the Mandarin Oriental Hotel on Tuesday morning.
"They will then travel with the President and Madame Peng to Horse Guards Parade, where the President will receive a Ceremonial Welcome. Their Royal Highnesses will attend the lunch at Buckingham Palace and receive the President and Madame Peng at Clarence House for tea."
Officials are particularly keen to ensure the visit goes well. It is an important one for the Government and aimed at deepening Britain's ties with the world's second-largest economy.
UK-China relations were briefly thrust into the deep-freeze after Prime Minister David Cameron's meeting with the Dalai Lama in 2012 prompted outrage in Beijing.
Chancellor George Osborne has just returned from a charm offensive to China designed to open up new markets for British companies.
Charles's thoughts on China's past leadership are well known after he described them as ''appalling old waxworks'' in extracts from his journal after he visited Hong Kong in 1997 for the handover ceremony.
His non-attendance at state banquets for Chinese leaders in the UK has been problematic in the past.
In 1999, the Prince was accused of boycotting a Chinese state visit to the UK by failing to attend the return banquet held for the then-president Jiang Zemin, who two years earlier attended the Hong Kong ceremony.
Charles's former aide Mark Bolland later revealed it was "a deliberate snub", adding: "He did not approve of the Chinese regime, and is a great supporter of the Dalai Lama, whom he views as being oppressed by the Chinese."
During president Hu Jintao's state visit in 2005, Charles carefully side-stepped the issue by being out of the country on a tour of the US on the night of the official dinner. He did not meet Mr Hu on the remaining two days of his visit.
But four years later, the relationship appeared to be changing and Charles held his first private meeting with a Chinese president in the UK.
He sat down for talks with Mr Hu at the Mandarin Oriental Hotel in London, and broached the delicate issue of Tibet.
In 2009 he opened The Prince's Charities Foundation (China) in Beijing - his first charity to be based in the country.
The Prince and the Dalai Lama have met a number of times over the years, but it is not known if they sat down for talks when the spiritual leader appeared at the Glastonbury festival this summer.
Protesters are planning to target the president's stay. The last incoming Chinese state visit was 10 years ago when hundreds of campaigners took to the streets to demonstrate against the country's poor human rights record and its long-standing occupation of Tibet.
Protesters from the Free Tibet group, as well as those supporting persecuted Uyghur Muslims, will use next week's trip to highlight their causes.
The day before the visit begins, Fabian Hamilton, chair of the All Party Parliamentary Group for Tibet, will host a Stateless Lunch in the Palace of Westminster to honour Tibetan, Uyghur and Chinese human rights defenders who have been imprisoned and intimidated by the Chinese government.