Although some effort has been made to reach an empirical consensus on the structure of agreeableness (Crowe, Lynam, & Miller, 2017; Davies, 2014), research exploring how facets of agreeableness relate to important psychological outcomes is lacking. Two studies were conducted to address these issues. In Study 1, in a large sample of 722 participants, we carried out an exploratory factor analysis and confirmatory factor analysis on agreeableness items from the International Personality Item Pool (IPIP; Goldberg, 2006) to determine the lower-order structure of agreeableness and examined whether the facets were differentially related to cognitive outcomes. In Study 2, in an international Amazon Mturk sample of 610 individuals, we used a five-factor model of agreeableness to examine broad- and facet-level relationships among agreeableness, its facets, psychopathology subfactors, and personality disorder domains in a smaller set of items from the IPIP NEO and IPIP HEXACO. Results from both studies highlight the potential importance of the facet of compassion in the realm of cognitive abilities. Study 2 demonstrated several positive and negative relationships among facets and psychopathology. Implications on the significance of facet-level analysis are discussed from both applied and basic research perspectives.