The Chief Secretary to the Treasury, who is leading negotiations with the unions, insisted the Government's offer was "good and generous" and warned the strike will make agreement more difficult.
Another senior figure, Cabinet Office Minister Francis Maude, also weighed into the row - calling the walkout "stupid and wrong".
Tuesday's action, which involves 33 unions, could see around two million people in total stay away from work including 18,000 immigration officials.
Sky sources say the military has been asked to prepare to man Britain's borders because of the strike, with civil servants also warned they may need to help out.
Mr Alexander, speaking to The Guardian newspaper, said: "What frustrates me a lot is that we're having these discussions centrally with the TUC and in individual schemes and they're making progress.
"The strike action... is both a distraction to that process and also a risk to it in the sense that, obviously, part of going on strike will harden opinions on the union side and might make it harder for them to sell a deal to their members when in fact I think we've got the basis of an agreement that is a pretty good deal for both sides."
He added: "I believe that many unions I talk to are serious and sincere about their desire to reach an agreement, but they are obviously going to have to persuade their own members who they've marched up this hill that in fact the agreement and the nature of the deal on offer is a good one."
Mr Maude, in an interview with the Daily Telegraph, warned trade union laws could be rewritten to make it more difficult to stage industrial action in future unless it had overwhelming backing from union members.
"If very disruptive strike action is carried out on the basis of these weak ballots, weak turnouts, the case for reform gets stronger," he said.
He suggested stopping unions from striking after ballots with low turnouts or a rule forcing action to be taken within a certain time after a poll could be considered.
The Government has warned the 24-hour walkout next week could cost the already fragile economy half a billion pounds and lead to job losses.
It is set to cause chaos at Heathrow Airport, where bosses have warned passengers they could face "gridlock" and be forced to wait on planes if terminals are overcrowded.
Airlines have been asked to dramatically cut the number of passengers flying to the UK's busiests airport because of the anticipated problems.
Operator BAA has written to carriers suggesting a 50% reduction in numbers on each international flight arriving into Heathrow on November 30.
Travellers have been warned they could face queues lasting 12 hours and airlines were warned of "mass cancellations" of departing aircraft.
In a letter, BAA's Heathrow chief operating officer Norman Boivin said the operator had "reluctantly concluded" the UK Border Agency would be unable to provide a contingency plan to cope with the walkout.
On Thursday, Prime Minister David Cameron condemned the planned industrial action and said there should be no doubt in voters' minds the fault lies with union bosses
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