Classroom size, curriculum, and student attendance are all important factors that affect student outcomes, but these factors cannot compare to the classroom teacher's influence on student academic performance. Unfortunately, highly qualified teachers are not equally effective in different school settings. Findings associated with highly effective teachers have suggested that testing personality characteristics could be a way to identify teacher effectiveness at the time of hire. This quantitative non-experimental (descriptive and correlational) study examined the relationship of specific personality characteristics among 22 highly effective teachers (14 urban and eight suburban), measured by the 44-item Big Five Inventory (BFI). The results described both groups' personality characteristics as very high Extroversion, very high Agreeableness, very high Conscientiousness, very high Openness, and low to average Neuroticism. The results answer the following research question: What is the relationship between the personality characteristics (measured by the BFI) and the school location of highly effective teachers? The results showed that Agreeableness, Conscientiousness, and Openness have an influence on teaching effectiveness in the urban and suburban settings. In practice, the 44-item BFI can be used to evaluate specific personality characteristics in urban and suburban settings during the teacher applicants' process. The following are appended: (1) 44-Item Big Five Inventory; (2) Power Sample Calculation; (3) Informed Consent Form; (4) Scoring; (5) Sample Size; (6) Comparison Sample: Means and Standard Deviations for BFI; and (7) BFI Approval.