If it's only overflowing when the boilers on, my guess is that the level when cold is too high, so when the water expands slightly when it heats up (as it's meant to), it's pushing the level just too high and going out your overflow.
As has already been said - check the level when cold, it might be your ballcock valve needs adjusting (you normally either just bend them, or sometimes you can move the actual float part up or down with a screw). Also check that the float hasn't got water in it, as sometimes they develop a hole - if this is the case, get a new one (should cost under a quid, as you can just replace the float part)...
A couple of other possibilities that come to mind are:
If you have a hot water cylinder, the coil may have a hole in it, causing the supply that is feeding the cylinder to force it's way back up through the heating pipes into your expansion tank (unlikely though as this would happen all the time, not just when your boiler is operating)
You might have a blockage in a pipe somewhere which is causing your pump to force water through the expansion pipe (do you have any cold radiators etc?)