: Can I make use of my wife's unused personal tax free allowance to reduce our income tax? I'm working full time (UK) and my wife is unemployed. Is there a way (legal of course!) for us to take advantage of her personal tax

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As DJClayworth's answer explains, normally you can't transfer personal allowances between people, whether married or not.
However, as of April 2015, it's now possible to transfer a small part of your allowance to your husband or wife under certain circumstances. The main criteria are that

One spouse needs to be earning less than the personal allowance
The other spouse needs to be paying basic rate tax only

The amount of allowance that you can transfer for the 2015-16 tax year is up to £1,060, so your spouse would end up saving £212 in tax at the 20% rate.
The full conditions are here:

You’ll be able to claim Marriage Allowance if all the following apply:

you’re married or in a civil partnership

your annual income is £10,600 or less, plus up to £5,000 of tax-free savings interest

your partner’s annual income is between £10,601 and £42,385

you were born on or after 6 April 1935

(for people born before 6 April 1935, there's a separate but confusingly similarly named "Married Couple's allowance")

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I wasn't going to answer this as I have only superficial knowledge. But since nobody else has, here is what I believe to be the case.

No, there is no simple tax accounting way of doing this. Once upon a time there was a 'married person's allowance' which essentially allowed you to claim more if you had a non-taxpaying spouse, but I believe that has been ended for people born after 1933.

The way people often try to make this happen is to pay their spouse for some kind of work, and then claim the payment as an expense. However the Inland Revenue is of course on to this. You will get away with it only if it is work that is real and necessary to your business; so you might be able to make it work for bookkeeping, but not for cleaning. And she would really have to do the work. And expect to be audited heavily if you try it.

TL;DR No