Probably something else - the route of the control signal to turn the boiler on in CH only mode is shown here...
http://www.gasheating.co.uk/Mid-Position-Valve.html
From the timer/programmer to the room stat and then to the Mid Position Valve - the Mid Position Valve motors over to the CH position and makes a microswitch. The fire-up signal is then routed to the boiler from the microswitch on an orange wire - but only when the motor has moved the valve and made the microswitch.
If the motor in the MPV fails or the valve sticks or the Microswitch fails then CH only will not work.
When Both CH & DHW are called for together the circumstances are different.
Good luck...
Peccavi
April 2010