Using a sample drawn from a Brazilian electric company exposing employees to both dangerous and non-dangerous working conditions, the current study provides evidence on the differential underlying mechanisms guiding the relationships of organizational identification and person-organization-fit (P-O fit) with job performance. We suggest that despite their relatedness in current literature, organizational identification operates as a largely self-centered process and P-O fit as a predominantly context-dependent one, leading to distinct work-related processes deriving from each construct. Our findings suggest that P-O fit serves as a pathway through which job identification induces job performance. In this mediating path, personality and in particular neuroticism, hinders the effects of identification, whereas job dangerousness, a contextual factor, undermines work-related effects of perceived environmental congruence (P-O fit). Discussing these results, we provide novel insights on the distinct mechanisms driving organizational identification, P-O fit and their contingencies.