Set Appliance State:

Isolate Mains Power to appliance as per TOPs P4
Set Multimeter to mVolts DC Set meter to measure DC mVolts
If pilot is extinguished 3 minutes must elapse before attempting to re-light
Attach +ve probe of multimeter to a suitable earth point via crocodile clip
Gas On

Measurement:

Depress gas valve control knob and ignite pilot.
Whilst keeping gas valve depressed, place -ve probe on the thermocouple where it connects with the interrupter plate, measure voltage produced by the thermocouple.