Background: This study intended to explore the role of personality traits and basic psychological needs in law enforcement officers’ ability to recognize emotions: anger, joy, sadness, fear, surprise, disgust, and neutral. It was significant to analyze law enforcement officers’ emotion recognition and the contributing factors, as this field has been under-researched despite increased excessive force use by officers in many countries. Methods: This study applied the Big Five–2 (BFI-2), the Basic Psychological Needs Satisfaction and Frustration Scale (BPNSFS), and the Karolinska Directed Emotional Faces set of stimuli (KDEF). The data was gathered using an online questionnaire provided directly to law enforcement agencies. A total of 154 law enforcement officers participated in the study, 50.65% were females, and 49.35% were males. The mean age was 41.2 (age range = 22–61). In order to analyze the data, SEM and multiple linear regression methods were used. Results: This study analyzed variables of motion recognition, personality traits, and needs satisfaction and confirmed that law enforcement officers’ personality traits play a significant role in emotion recognition. Respondents’ agreeableness significantly predicted increased overall emotion recognition; conscientiousness predicted increased anger recognition; joy recognition was significantly predicted by extraversion, neuroticism, and agreeableness. This study also confirmed that law enforcement officers’ basic psychological needs satisfaction/frustration play a significant role in emotion recognition. Respondents’ relatedness satisfaction significantly predicted increased overall emotion recognition, fear recognition, joy recognition, and sadness recognition. Relatedness frustration significantly predicted decreased anger recognition, surprise recognition, and neutral face recognition. Furthermore, this study confirmed links between law enforcement officers’ personality traits, satisfaction/frustration of basic psychological needs, and emotion recognition, χ2 = 57.924; df = 41; p = 0.042; TLI = 0.929; CFI = 0.956; RMSEA = 0.042 [0.009–0.065]. Discussion: The findings suggested that agreeableness, conscientiousness, extraversion, and neuroticism play an essential role in satisfaction and frustration of relatedness needs, which, subsequently, link to emotion recognition. Due to the relatively small sample size, the issues of validity/reliability of some instruments, and other limitations, the results of this study should preferably be regarded with concern.