Need for cognition (NFC) represents interindividual differences in tendencies to engage and enjoy cognitive endeavors. Exploratory information seeking (EIS) refers to individual tendencies to attain cognitive stimulation through acquiring information related to consumer products or services out of curiosity. The current study aims to provide an in-depth investigation of the relationship between NFC and EIS and extend this relation to determine neuroanatomical correlates of NFC and EIS. This study proposed two central hypotheses: (1) NFC and EIS scores are positively correlated and (2) the gray matter volume (GMV) of brain regions implicated in motivation, valuation, and reward systems are positively associated with both NFC and EIS. Self-report and structural MRI data of 91 Singaporean Chinese participants were utilized for the study. No statistically significant correlation was revealed between NFC and EIS scores. Neuroanatomical associations of the GMV of brain regions implicated in visuospatial, attentional, and reward processing with individual constructs of interest were explored. When examining NFC and EIS scores, larger GMV in the right pallidum and left fusiform gyrus was found in participants that reported higher levels of NFC (vs. lower NFC levels), larger GMV in the left precuneus in those with greater tendencies to engage in EIS (vs. lower EIS levels), and larger GMV of the left fusiform gyrus associated with greater endorsement of both NFC and EIS. When investigating the exploratory factor analysis-generated factors of NFC and EIS, similar patterns of associations were found between self-reported levels of agreement against factors and GMV of brain regions implicated. Correlational analysis and exploratory factor analysis indicated the absence of a relationship between NFC and EIS. Additionally, voxel-based morphometry whole-brain analysis revealed neuroanatomical correlates of the GMV of brain regions implicated in visuospatial, attentional, and reward processing with NFC and EIS.