The spatial and temporal distribution of the discharge streamers in positive pulsed wire-to-wire electrode configuration in atmospheric air is investigated by an electrical-optical diagnostic system. Time-resolved ICCD images show that the discharge streamers in wire-to-wire electrode develop in three phases: the primary streamer, the secondary positive streamer, and the secondary negative streamer. It is observed that the evolution of discharge streamers is strongly influenced by the amplitude of the applied voltage. The optical emission spectroscopy measurement of hydroxyl radical OH indicates that the OH is mainly generated in the secondary positive streamer near the anode region. But in the region near the cathode the emission of OH radicals can also be detected due to the secondary negative streamer. The influences of rise time, fall time and pulse duration on streamer dynamics and the subsequent radical production are observed. It is shown that the average propagation velocity of the primary streamer decreases with the increase of the rise time, while the variation of pulse width and pulse duration parameters have little effect on that of the primary streamer. The response surface methodology based on Box–Behnken design model is implemented to evaluate the contribution of the three critical pulse parameters on ozone production. The results of the response surface quadratic model show that the pulse rise time plays the most prominent role in the generation of ozone among the three pulse parameters of rise time, fall time and pulse duration.