In this paper, the surface discharge current pulses of PEEK (polyether-ether-ketone) under positive repetitive square voltage are measured. The effects of voltage rise time and fall time on pulse parameters of discharge current, instantaneous voltage of discharge and time-lag of discharge are analyzed in detail. The results show that the amplitude of discharge current and the instantaneous voltage of discharge decrease, and the time-lag of discharge and the dispersion of time-lag increase with the increase of voltage rise time. With the increase of voltage fall time, the amplitude of discharge current decreases and the instantaneous voltage of discharge, the time-lag of discharge and the dispersion of time-lag increase. To analyze the influence mechanism of voltage rise time and fall time on surface discharge, the accumulation of surface charge under repetitive square voltage is regarded as a periodic process. Besides, the correlation between forward discharge and back discharge in the process of discharge is analyzed, and the development of discharge is analyzed by using the time-lag theory. Furthermore, the relationship between instantaneous discharge voltage and voltage slew rate is revealed, and the surface charge accumulation processes under different voltage rise times and fall times are compared to reveal the influence mechanism of rise time and fall time on the surface discharge under positive repetitive square voltage.