Assume Combi. with diverter valve not working. May be pressure diaphragm has given way (cheap & simple to fix once diagnosed) or the microswitches operated by diaphragm have gone open/closed circuit. Typical symptoms are Set Heating plus Hot water (gives hot water for a while) or Set Hot water very slow heat & nearest radiators warm up when boiler set to hot water or Hot water much better if all rad valves closed.
Can replace entire assembly or once diverter valve removed, mark alignment, dismantle & check diaphragm (may be split), check that microswitches operate. Be sure to label/photograph wiring, completely isolate boiler electrically and shut off & drain boiler. You may find it difficult to access diverter valve pipe connections:- best to measure nuts & buy secondhand hefty spanners to fit the usually quite large nuts.
If unsure, the work should only be undertaken by a qualified professional.
Geoff Ipswich, April 2011