“Pocket rocket” healthcare assistant Adela Baldwin-White, 47, from Grimsby, died in an intensive care unit on Thursday after her condition worsened dramatically in a matter of days.
Her husband asked doctors if the vaccine could be used to save her life, but was told it was too late.
The first batches will be administered on Tuesday, with healthcare workers, particularly those working in care homes, due to be at the front of the queue.
She is one of at least 204 frontline health and care workers who have been identified by the PA news agency after dying with coronavirus – although some estimates put the figure above 600.
An emotional Lawrence Baldwin-White, 65, said he wished his wife had been able to take the life-saving jab before she got ill.
“I think it’s definitely better than the alternative. I know it’s an unknown, but the alternative… is to have to go through what myself and (their son) Eric are having to go through now.”
Mr and Mrs Baldwin-White met in 2004 in Cyprus, where she was working as a carer and he was visiting for a holiday.
After a whirlwind romance, he returned six months later and they married, moving to the UK together shortly after.
Before she caught Covid-19, Mrs Baldwin-White had been working in a rehabilitation unit for mental health trust Navigo, while also working shifts in care homes.
Originally from the Philippines, she was hugely popular with colleagues and earned a reputation as a “caring” and “irreplaceable” worker who “just inspired everyone”.
“She’s just a great person and she puts everyone else first,” Mr Baldwin-White told the PA news agency.
“Even when she went into hospital… she was still looking out for people instead of resting and trying to help other people,” he said.
A GoFundMe campaign set up by a former colleague of Mrs Baldwin-White has already raised more than £2,000 to help pay for her funeral, and was flooded with messages from people who knew and worked with her.
“The messages just keep coming in every minute, constantly, with the support,” said her son Eric Plando, 25, who also works for Navigo as a nursing assistant.
“Everyone’s supported us so much that it’s brought happiness in these times of trouble.”
Navigo said the news was “devastating”, calling Mrs Baldwin-White “a larger than life character, described fondly as a ‘pocket rocket’, someone staff could confide in and who was always there for others”.