The move means RMT members will not take part in any more strikes, ending the long-running dispute over pay, jobs and working conditions.
In a turnout of nearly 90 per cent, members voted by 76 per cent to 24 per cent in favour, signalling an end to the bitter row, which led to a series of strikes in recent months.
The union said the deal includes an uplift on salaries of between 14.4 per cent for the lowest paid grades to 9.2 per cent for the highest paid, increased backpay, a no compulsory redundancy agreement until January 2025 and rail travel benefits.
RMT general secretary Mick Lynch said: “Strike action and the inspiring solidarity and determination of members has secured new money and a new offer which has been clearly accepted by our members and that dispute is now over.
“Our dispute with the train operating companies remains firmly on and our members’ recent highly effective strike action across the 14 train companies has shown their determination to secure a better deal.
“If the Government now allows the train companies to make the right offer, we can then put that to our members, but until then the strike action scheduled for March 30 and April 1 will take place.
“The ball is in the Government’s court.”
Transport Secretary Mark Harper said: “I am pleased Network Rail’s RMT members have voted to accept a fair and reasonable 5% plus 4% pay offer, over two years, that the Government worked hard to facilitate.
“While this is good news, unfortunately, RMT members who work for train operating companies are not being given the same chance to bring their dispute to an end. That’s because the RMT has refused to put the Rail Delivery Group’s very similar offer to a vote, denying these members the pay rise they deserve.
“That’s why I am once again urging the RMT to call off their upcoming strikes across train operating companies, put the Rail Delivery Group offer to a vote, and give all of their members a say.”