Married couples risk missing out on up to £1,250, Martin Lewis warned.
The MoneySavingExpert founder said around 2million Brits aren't claiming marriage tax allowance.
The tax allows you to transfer £1,260 of your personal allowance to your partner to cut their yearly tax bill.
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Your personal allowance is the amount you can receive tax-free each financial year.
For the current 2022/23 year, the tax break you can get is worth £252, but it's possible to claim all four previous years.
If you claim for this tax year and backdate the maximum four years, you can receive up to £1,242.
You'd need to be married or in a civil partnership to claim and both of you must be born on or after April 6, 1935.
One of you needs to be a non-taxpayer, while the other needs to be paying the basic 20% rate of tax.
It usually means one of you earns less than £12,570, while the other makes between £12,571 and £50,270.
Martin urged people on Twitter to claim now if they're eligible for marriage tax allowance.
The end of the current tax year is on Wednesday (April 5) and after this, you'll be able to backdate your claim to the 2019/20 tax year.
Currently, you can go as far back as the 2018/2019 tax year.
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He said: "URGENT please share. Are you married or in civil partnership if so – is one of you a basic 20% taxpayer?
"The other a non-taxpayer (earn under £12,570/yr). If so you're likely due up to £1,300 tax back, but if you don't sort by Wednesday April 5 you risk losing £100s.
"Many asking me 'We're pensioners can we do this', 'I'm a volunteer can I do this', 'I'm on maternity can I do this', 'I'm self employed can I do this', YES!
"It's simple, if you're under 85, and in a tax-year don't pay tax, then you can give this to your 20% tax rate paying spouse."
You can apply for marriage tax allowance through the HMRC website or by calling 0300 200 3300.
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