Academic achievement of the pupil is the prime concern of educational process. The problem solving ability has been playing a significant role in determining student’s academic achievement. Keeping this in view, the present study was designed to examine empirically the effect of problem solving ability on the academic achievement of rural and urban school students. The research was conducted on 250 school students (118 rural & 132 urban) studying in 10th class CBSE affiliated private schools that were randomly selected from Rohtak district of Haryana State. Descriptive survey method was used to elicit opinion of rural & urban school students about their problem solving ability and their academic achievement at school. The problem solving ability of sample was assessed by using Dubey’s Problem Solving Ability Test (2006) & for academic achievement of students, the school records i.e. marks obtained by the students in previous (IXth) class was considered. The data was analyzed statistically by using ANOVA supplemented by t-test. The findings of the study revealed that problem solving ability had significant effect on the academic achievement of the students whereas significant difference was observed in the academic achievement of students studied in urban and rural schools. However, the significant interaction effects of locality and problem solving ability on the academic achievement of the students had been found.