Background: Our objective was to evaluate carotenoid accumulation in bell peppers during shelf life under different light conditions. Methods: Fruit stored for 6 d at 7 °C received a 9 kJ m−2 UV-B treatment, while non-UV-treated were used as control (CTRL). Subsequently, all peppers were disposed for a retail sale period of 4 d at 20 °C with a photoperiod of 14 h under fluorescent light (FL) + 10 h under darkness (D), FL, or blue + red LEDs (BR LED). Results: Total antioxidant capacity (TAC) was increased by the UV-B treatment and the photoperiods supplemented with FL and BR LED, which was directly related to the carotenoid content. In fact, CTRL peppers (225 mg β-carotene kg−1) under FL+BR LED showed an increase of ~33% of 13-cis-β-carotene, ~24% of all-trans-β-carotene, and ~27.5% of 9-cis-β-carotene compared to FL + D and FL + FL. Capsaicinoids showed an increase by ~22%, ~38%, and ~27% in the content of capsanthin, capsanthin laurate, and capsanthin esters, respectively, after the UV-B treatment, which was even enhanced after the LED-supplemented photoperiod by ~18% compared to FL+D. Conclusions: Illumination with BR LEDs + UV-B during the retail sale period nights is recommended to increase the bioactive content of bell peppers via carotenoid accumulation to 270 mg β-carotene kg−1.