Ciprofloxacin, as a second generation of fluoroquinolone antibiotics, has been proved to cause environmental harm and exhibits toxic effects on the wastewater and surface water even at low concentrations due to their continuous input and persistence. Despite tremendous efforts, developing ciprofloxacin detection method with accuracy and sensitivity at low-cost remains a great challenge. Herein, graphitic carbon nitride/BiOCl composite (g-CN/BiOCl) has been designed for a facile and sensitive photoelectrochemical (PEC) monitoring platform of ciprofloxacin at first time. BiOCl can be modified with the g-CN nanosheets which are obtained via solvothermal process at low-temperature conditions. The use of g-CN is shown to strongly enhance the PEC response of BiOCl due to the formation of heterojunctions. The photocurrent generated at the g-CN/BiOCl-modified ITO (with 13 wt% g-CN content) is much higher and more stable than that of a BiOCl-modified ITO. Based on these findings, the g-CN/BiOCl-modified ITO was used to design a PEC assay for the antibiotic ciprofloxacin. Furthermore, the limit of detection of the ciprofloxacin PEC sensor has been significantly lowered to 0.2 ng mL−1. In addition, the PEC sensor can detect ciprofloxacin in the wide range of 0.5–1840 ng mL−1.