Penicillium digitatum is the causal agent of green mold, a primary postharvest disease of citrus fruits. This study evaluated the efficacy of a novel photoactive chitosan–riboflavin bioconjugate (CH-RF) to control green mold in vitro and in lemon fruit. The results showed total inhibition of P. digitatum growth on APDA supplemented with CH-RF at 0.5% (w/v) and a significant reduction of 84.8% at 0.25% (w/v). Lemons treated with CH-RF and kept under controlled conditions (20 °C and 90–95% relative humidity) exhibited a noteworthy reduction in green mold incidence four days post-inoculation. Notably, these effects persisted, with all treatments remaining significantly distinct from the control group until day 14. Furthermore, CH-RF showed high control of green mold in lemons after 20 days of cold storage (5 ± 1 °C). The disease incidence five days after cold storage indicated significant differences from the values observed in the control. Most CH-RF treatments showed enhanced control of green mold when riboflavin was activated by white-light exposure. These findings suggest that this novel fungicide could be a viable alternative to conventional synthetic fungicides, allowing more sustainable management of lemon fruit diseases.