The utilization of light-conversion films (LCFs) to enhance natural photosynthesis is attracting much attention in the field of agricultural planting toward increasing crop yields. However, the working efficiency of most light-conversion materials is seriously limited by the narrow light-harvesting range and poor compatibility with the involved matrix. Herein, in the contribution, the boron/nitrogen-codoped carbon dots (BN-CDs) with remarkable dual-emission performance and high photoluminescence quantum yield are purposefully designed and solvothermally fabricated as both a light-conversion agent and nano reinforcements and then integrated with the biodegradable poly(vinyl alcohol) (PVA)−starch composite matrix (PSC) to smartly construct a sustainable LCF (i.e., BN-CDs/PSC film). The dual-emission origin of BN-CDs is rationally proposed as well. More remarkably, besides excellent optical properties, environmental compatibility, mechanical properties, reusability, and water resistance, the achieved high-quality BN-CDs/PSC films are endowed with a powerful capability to efficiently convert ultraviolet light to blue and red light, boosting the utilization of solar energy. When evaluated as a commercializable LCF, the optimized BN-CDs/PSC-2 film exhibits appealing promotion in the growth and chlorophyll content of mung bean sprouts. More meaningfully, our rationally designed BN-CDs/PSC films hold enormous promise in extensive applications in high-efficiency agricultural planting.