The current position is that hours spent on call away from the workplace, where the employee is free to pursue leisure activities, only count as working time for that time which is actually spent undertaking normal duties. Where time on call has to be spent at the workplace, however, the European Court of Justice has ruled (in the SiMAP and Jaeger cases) that this counts as working time, whether or not the employee is actually working. The British government is still arguing for a change in EU law to allow for a more precise definition of working time (or non-working time) under such circumstances, but meanwhile the sensible course is to keep on call time on the premises down to a minimum.
If you believe that you might have a problem in this regard, you should take specific legal advice as soon as possible, since the cost of ignoring it could be very high.