To control the excessive dechlorination of polychloronitrobenzene hydrogenation to produce polychloroaniline,the effects of nitric acid concentration,catalyst reduction temperature and time in the preparation of Pd/C catalyst on the Pd particle size and catalytic hydrogenation activity and selectivity are investigated.The results indicate that the Pd/C catalytic activity decreases as the Pd particle sizes increase,and the catalyst selectivity goes up;the dispersion and particle sizes of Pd go up first and then down with the increase of nitric acid concentration;the elevated reduction temperature and time yields larger Pd particles;the optimal Pd catalyst with the particle sizes from 16 to 20 nm can be prepared on 15% nitric acid by reduction under hydrogen atmosphere at 200~250 ℃ for 4~5 h;the catalyst shows relatively high hydrogenation activity and selectivity in the hydrogenation reduction of polychloronitrobenzene;the yield can reach more than 99% and the selectivity for pentachloroaniline can reach above 96%.