Photoelectrocatalytic technology has proven to be an efficient way of degrading organic contaminants, including dyes. Graphene (GR) -based catalysts have been frequently used in photoelectrocatalysis, due to their excellent catalytic performances. In this work, the GR/beta-cyclodextrin (GR/β-CD) composite was prepared and used for a widely used triphenylmethane dye (bromophenol blue, BPB) photoelectrocatalytic degradation. The results indicated that the degradation of the prepared GR/β-CD composite for BPB was effective with the combination of external bias voltage and simulated sunlight irradiation. Under optimum conditions, the BPB (10 mg L⁻¹) was completely eliminated by GR/β-CD composite within 120 min. ˙O₂⁻ played a prominent role in the BPB photoelectrocatalytic degradation. The time required for the removal of BPB in water to reach 100% can be reduced to 30 min with the presence of Cl⁻, owing to the generation of ˙Cl. Moreover, the toxicity of the degraded system with Cl⁻, predicted by the QSAR (Quantitative Structure–Activity Relationship) model in ECOSAR (Ecological Structure–Activity Relationships) program, was weaker than that without Cl⁻. The prepared GR/β-CD composite revealed great advantages in photoelectrocatalytic degradation of organic pollutants due to its metal-free, low cost, simplicity, and efficient performance. This work provided new insight into the efficient and safe degradation of organic pollutants in wastewaters.