I'm due to collect my new car early March, however the tax runs out at the end of February on the old one, so I was considering setting up the online payments to pay monthly to get around this. Am I able to do that? I mean tax for just a month before I declare the car sold and no longer my responsibility (dvla documents withstanding)

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You can claim back any full months tax - which I believe is issued automatically when the DVLA receive confirmation that you are no longer the registered keeper of the vehicle

I had to tax my old car for 2 and a half months before collecting the new one, but I stuck a year on it just because the monthly cost is lower that way. As said above you get unused months back in full, so even for 1 month it would work out cheaper paying 12 then getting 11 back rather than paying 1 at a higher price. Worth considering!