Partial discharges (PDs) in electrical equipment are normally detected with 50 Hz AC sinusoidal voltage stimulus in an online situation, but can also be measured at other non-sinusoidal and non-power frequency stimuli in off-line situations. In this work, three types of non-sinusoidal voltage waveforms, which are symmetric triangular-wave, symmetric trapezoidal-wave, and approximately square-wave voltages, were applied to investigate the effect of ambient temperature on the PD activity produced in an air gap between mica-epoxy surfaces, in combination with the frequency-domain dielectric spectroscopy (FDS) measurement of mica-epoxy dielectric. The results show that the PD inception voltage (PDIV) decreases greatly with the increase of temperature at three types of applied voltages. The PD behavior at symmetric triangular-wave and sinusoidal-wave voltages shows no obvious changing with the increase of temperature. With the increase of ambient temperature, the average PD charge exhibits regular increasing trend and the increment has almost proportional relation with the increasing rate of applied voltage; the maximum PD charge has the largest value at approximately square-wave voltage and also shows the increasing trend. The most obvious effect of temperature on PD activity lies in the constant voltage period of applied voltage. In this period, the average PD number and average PD charge both exhibit almost exponential increasing trend with the increase of temperature.