The purpose of this study is to identify academically at-risk students in first-semester general chemistry using affective characteristics via cluster analysis. Through the clustering of six preselected affective variables, three distinct affective groups were identified: low (at-risk), medium, and high. Students in the low affective group reported lower scores on intellectual accessibility, emotional satisfaction, math self-concept, chemistry self-concept, and self-efficacy and a higher score on test anxiety. Significant differences were found on exam performance between the high and low affective groups with the high affective group performing significantly better than the low affective group. In terms of value beliefs, expectancy beliefs, and metacognitive self-regulation, differences were found between the high and low groups as well. These findings provide instructors an efficient way of identifying and reaching out to at-risk students early in the semester, as well as gaining a better understanding of the affective profile found in general chemistry.