The country's biggest rail union has been warned by Transport Secretary Grant Shapps that this week's strikes will be a "huge act of self-harm" which could jeopardise the future of the industry.
A call from the Rail, Maritime and Transport (RMT) union for the Government to intervene as a "stunt" was dismissed by Mr Shapps, saying the union had been "gunning" for industrial action for weeks.
However, Labour said ministers needed to step in to prevent the network "grinding to a halt" in a dispute over pay, conditions and job losses.
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Industry bosses insisted that a settlement is still possible - with further talks taking place on Monday - but that the union had to accept the need for reform of "outdated" working practices, the PA news agency reported.
Steve Montgomery, the chairman of the Rail Delivery Group, told the BBC: "We are now meeting them again tomorrow. We do want to offer them something but we have to have reform.
"There is room for compromise. We have got to work together, but we can resolve it. This is resolvable."
On Saturday, the RMT confirmed that strikes at Network Rail and 13 train operators will go ahead on Tuesday, Thursday and next Saturday, and on London Underground on Tuesday.
General secretary Mick Lynch said the union had no choice but to act after the train operators had still not made a pay offer when talks adjourned on Thursday.
"We have to fight this because we haven't had any pay rises, we are faced with thousands of job cuts and they want to rip up our terms and conditions in a form of hire and re-hire that is internal to the railway," he told Sky News's Sophy Ridge on Sunday programme.
He warned that industrial action would continue if there was no settlement with other rail unions balloting their members on strike action.
"If there is not a settlement we will continue our campaign. I think there are going to be many more unions balloting across the country because people can't take it any more," he said.
Mr Shapps, however, said the union had been "gunning" for industrial action for weeks and accused it of "punishing" millions of "innocent people" who will be affected by the strikes.
"Of course, it is a reality that if we can't get these railways modernised, if we can't get the kind of efficiency that will mean that they can work on behalf of the travelling public, then of course it is jeopardising the future of the railway itself," he told the Sophy Ridge on Sunday programme.
"I think it is a huge act of self-harm to go on strike at the moment. I don't believe the workers are anywhere near as militant as their unions who are leading them up the garden path. They are gunning for this strike. It is completely unnecessary."
For Labour, shadow communities secretary Lisa Nandy said that only the Government could now resolve the dispute and prevent the strikes going ahead.
"The biggest problem that this country has is not militant workers, it's a militant Government," she said.
In a speech to the Labour Local Government Association conference in Warwick, Sir Keir Starmer said ministers wanted to see the country "grind to a halt" so they could "feed off the division".
"Instead of grown-up conversations to take the heat out of the situation, they are pouring petrol on the fire," the Labour leader said.
"Instead of bringing people together in the national interest, they are stoking division in their political interest."
Mr Shapps dismissed the claim, telling the BBC's Sunday Morning programme that many people would find the comments "pretty offensive".
However, the calls for the Government to intervene were joined by former minister Jake Berry, the leader of the Northern Research Group of Tory MPs, who said ministers needed to avoid widespread disruption.
"By training I'm a lawyer and I can tell you that the only way out of a dispute is via negotiation," he told Times Radio.
"I call on all parties, including the Government, to get around the table because it's going to have a huge negative impact on people's lives."
