The ozonation efficiency for removal of recalcitrant organic pollutants in alkaline wastewater is always low because of the presence of some hydroxyl radical scavengers. To solve this problem, the O3/Ca(OH)2 system was put forward, and p-nitrophenol (PNP) was chosen to explore the mechanism of this system. The effects of key operational parameters were studied respectively; the Ca(OH)2 dosage 3 g/L, ozone inlet flow rate 3.5 L/min, ozone concentration 65 mg/L, reactor pressure 0.25 MPa, and temperature 25 °C were obtained as the optimal operating conditions. After 60 min treatment, the organic matter mineralized completely, which was higher than the sum of the ozonation-alone process (55.63%) and the Ca(OH)2 process (3.53%). It suggests that the calcium hydroxide in the O3/Ca(OH)2 process possessed a paramount role in the removal of PNP. The liquid samples and the precipitated substances were analyzed by gas chromatography mass spectrometry, X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectrosopy; it was demonstrated that Ca(OH)2 could accelerate the generation of hydroxyl radical and simultaneously in situ separate partial intermediate products and CO32− ions through some precipitation reactions.