The British Medical Association (BMA) is pushing ahead with a ballot for possible strikes after it rejected a last-ditch pay offer by Health Secretary Jeremy Hunt.
The union has refused to get back around the negotiating table with the Government in the row over a new contract, which is set to be imposed from next summer on doctors working up to consultant level.
The BMA has issued members with papers over possible action in a ballot that will run until November 18.
Mr Hunt made a bid to avert strikes on Tuesday evening with a fresh deal, including an 11% rise in basic pay and overtime pay after 7pm on Saturday evenings, a concession on the previous 10pm.
Flexible pay premiums would be applied to more specialities than just general practice and A&E care, with acute medical ward staff and psychiatrists benefiting, he said.
Mr Hunt argued that just 1% of doctors would lose pay because of the deal and those were limited to doctors working too many hours already.
He said maximum working hours per week would fall from 91 to 72 under the new deal.
Johann Malawana, the BMA's junior doctor committee chairman, said the increase in basic pay was misleading as it would be "offset by changes to pay for unsocial hours - devaluing the vital work junior doctors do at evenings and weekends".
He added: "While in the short-term existing junior doctors may have their pay protected, protections will only exist for a limited time.
"Without the reasonable assurances junior doctors require, the BMA has been left with little option but to continue with plans to ballot members on industrial action.
"This is not a decision we take lightly. However, the Government's refusal to work with us through genuine negotiations, and its continued threat to impose an unsafe and unfair contract, leaves us with no alternative."
During the ballot, doctors will respond to two questions: whether they are prepared to take part in a strike and whether they are prepared to take industrial action short of striking.
The BMA has proposed to stage emergency care-only action in the first instance, with junior doctors providing the same level of service as they would do on Christmas Day.
But there is the possibility of all trainees in England withdrawing their labour, the union said.