Authorities saddled with responsibility of maintaining internal security of the Nigerian state have come under criticism due to incessant security breaches that have resulted into killings of Nigerians. Thus, the purpose of this research was to explored moderated mediation effects of intrinsic factors and polychronicity on the relationship between work environment and work performance among personnel of the Nigeria Police Force. In order to test all the three hypotheses formulated for the study, a total of 450 personnel of the Nigerian Police Force, Osun State Command, south western Nigeria were selected through systematic sampling technique. The survey yielded 68% usable response rate and regression analysis was performed on the primary data collected from 306 respondents which constituted usable responses with the help of Analysis of Moment Structure (AMOS) adapted on the Statistical Package for Social Scientist (SPSS) version 23. The results of data analysis revealed significant relationship between work environment and work performance among staff of Nigeria Police Force; and preference for polychronicity by policemen significantly mediated relationship between work environment and work performance. Additionally, intrinsic factors significantly moderated relationship between work environment and polychronicity, and thus by extension the collected data confirmed the model of moderated mediation earlier proposed. In order to maximize job and organizational performance, Nigeria Police Service Commission would have to create work environment that encourages multitasking through appropriate intrinsic motivating factors.