yes but you can't simply pool them and go 'voilla!'

You need to be able to charge whole sectors to each account.,

So if a sector was 12.5 k miles you could use hers for one sector and yours for the rest. But if it was 40k you couldn't

You could transfer her miles to your account but that costs £ and it could be cheaper just to buy them for your account.

Your wife would need to call VS and make you an authorised user of her account as well.