Background and Objectives: Little is known regarding the 5C psychological antecedents to COVID-19 vaccination among pharmacists in low- and middle-income countries. This study aimed to assess the acceptance of COVID-19 vaccination and its psychological antecedents among community pharmacists in Khartoum State, Sudan. Materials and Methods: A cross-sectional study was conducted from July to September 2022. A self-administered questionnaire was used to collect data about sociodemographic and health status characteristics, vaccine acceptance, and the 5C psychological antecedents to vaccination. Stepwise logistic regression analysis was conducted, and results were presented using odds ratios (ORs) and their corresponding 95% confidence intervals (CIs). Results: A total of 382 community pharmacists participated in the current study, with a mean age of 30.4 ± 5.6 years. Nearly two-thirds of the participants (65.4%) were females, and the majority (74.9%) have received or intended to receive the COVID-19 vaccination. Vaccine acceptance was significantly associated with the following psychological antecedents to vaccination: confidence, complacency, constraints, and calculation (p < 0.001). Results of the logistic regression showed that confidence in vaccines [OR = 6.82 (95% CI = 3.14–14.80)], conspiracy beliefs [OR = 0.44 (95% CI = 0.23–0.85)], and constraints to vaccination [OR = 0.18 (95% CI = 0.06–0.56)] were the significant determinants of vaccine acceptance. Conclusion: The study revealed important predictors of COVID-19 vaccine acceptance that can be used to guide policymakers in designing target-oriented interventions that can improve the vaccine acceptance rate among community pharmacists in Sudan. These findings suggest that interventions to promote vaccine acceptance among pharmacists should focus on building confidence in vaccines and providing accurate information about the safety and efficacy of the COVID-19 vaccine, and reducing constraints to vaccination.