The wireless stat only controls the CH, not the HW. The HW would still be controlled by the timer (and also a HW stat which is really just there to shut off the boiler, to stop the water getting too hot).
I did exactly what you are describing recently. I got a two-channel clock (Honeywell ST6400C) and a wireless stat (Honeywell CM67). The ST6400C turns the hot water on or off independently of the room stat turning the heating on and off. On the ST6400 timeclock I've programmed the heating to be "always on"; the CM67 is connected in series so the heating is only on when the stat requests it.
The secret to making it all work is to get a mid-position three-port valve.
It would be very handy to have a stat combined with a wireless programmer which would allow you to control everything from one place, but nobody seems to make anything like this.
Yeah, but that's not as efficient as having more precise control, which you can have by marrying a two-channel programmer and a stat as described above.