A pulsed discharge plasma-TiO2 catalytic (PDPTC) system was developed to investigate the degradation of p-nitrophenol (PNP) in soil. The effects of TiO2 amount, soil pH and air moisture on PNP degradation were evaluated, and PNP degradation processes were predicted with Gaussian 03W combined with density functional theory (DFT). Experimental results showed that 88.8% of PNP could be smoothly removed in 10 min in the PDPTC system with the specific energy density of 694 J g(soil)(-1), compared with 78.1% in plasma alone system. The optimum TiO2 amount was 2% in the present study, and higher TiO2 amount exhibited an inhibitive effect. Alkaline soil was favorable for PNP removal. The increase of air moisture to a certain extent could enhance PNP removal. A OFT calculation presented that there was a high preference for the -ortho and -para positions with respect to the functional -OH group of PNP molecule for (OH)-O-center dot radicals attack. The main intermediates were hydroquinone, benzoquinone, catechol, phenol, benzo[d][1,2,3]trioxole, acetic acid, formic acid, NO2 center dot- NO3- and oxalic acid. The generation of hydroxylated intermediates, NO2- and NO3- suggested that the experimental results were consistent with those of the theoretical prediction. (C) 2011 Elsevier B.V. All rights reserved.