Phototrophic purple bacteria (PPB) are one group of dinitrogen (N2)-fixing bacteria often found in the anoxic and photic zone of paddy soil. In the present study, the effects of inoculation of PPB on grain yield of rice and changes in their populations and nitrogenase activity were investigated with and without surface application of rice straw in a pot experiment. As an inoculant, Rhodopseudomonas palustris strain KN122 isolated from a paddy soil was selected, and the cell suspension was inoculated into the floodwater once or three times during the cultivation. As a result, the inoculation of PPB increased the grain yield of rice. Compared to the control, the grain yield was 9% higher in the inoculated plot without rice straw application. The treatment was more effective in combination with rice straw application. In the plots where PPB were inoculated with rice straw, grain yields were 21% (single inoculation) and 29% (triple inoculation) higher. Populations of PPB in the plots without rice straw application significantly increased by the inoculation, unlike those in the plots with rice straw application, except for the bulk soil. Phototrophic and heterotrophic nitrogenase activities (acetylene-reducing activity) associated with the soils or residues of the rice straw were not affected by PPB inoculation throughout the experiment. This indicates that the inoculation of PPB into floodwater may not be effective for enhancing N2 fixation in paddy soils and that the beneficial effect of PPB inoculation on the grain yield of rice may be due to unidentified functions of PPB other than biological N2 fixation.