But if it was either sensor then surely it would overheat on DHW or CH whereas the OP says it works fine on both and does not overheat?
Hang on, we did another test last night - I think maybe it does overheat in CH/HW mode also:
CH/HW mode: -
CH light on
we turned the temperature right down on the CH dial as it was too hot in the house, and it decided to turn the CH off completely. Temp rose and boiler was bubbling, still with CH light off (even though we hadn't turned it off, just down).
Turned CH dial up again to see if it would 'kick in' but CH light would not come on. In the end we turned off the boiler completely.
Heating would not come on again this morning, but we used some hot water (this was really really hot), and the CH then decided to come on.