Objective: The current study investigated the internal structure and external relations of the Children’s Psychological Processes Scale (CPPS). Method: Principal components analysis and exploratory factor analysis were conducted. Concurrent validity studies were also completed with the Behavior Rating Inventory of Executive Function (BRIEF) and Woodcock–Johnson III Tests of Cognitive Abilities (WJ III COG). Results: A general cognitive ability factor was identified that accounted for up to 85% of the scale’s total variance. Exploratory factor analysis produced a three-factor solution that included general processing ability, executive functions, and visual-motor processing. Subscales comprising the CPPS executive functions factor were found to have high correlations with BRIEF composites and subscales. CPPS subscale correlations with comparable WJ III COG tests indicated that the majority of the CPPS subscales assess the same constructs as those measured by the WJ III COG. Conclusion: The results suggest that rating scale measures of cognitive and metacognitive processes assess the same latent factors and cognitive processes as performance-based measures.