You ONLY have hot water when the Central Heating is on?
There's a motorised valve that directs the heated water to either the taps or to the radiators depending on what your programmer is asking for. If both Heating and Water are selected it sits in a mid-position. Your motorised valve may be defective - call in an expert. - Many of them have a lever that you can use to move the valve position - you might try fiddling with it...
http://www.centralheating-diy.co.uk/images/3_port.jpg
Peccavi, April 2009