Fluoroquinolone antibiotics are widely used in daily life, but their abuse has caused serious problems, so it is very important to detect fluoroquinolones accurately and conveniently. In this study, a light-activated nanozyme sensor array (TiO2 NRs/CuO/rMIP) was prepared, and principal component analysis (PCA) was employed for qualitative and quantitative determination of four fluoroquinolones in water environments. The photoactive sites of TiO2 were determined by photo-deposition of CuO, and the molecularly imprinted sites was anchored to the photoactive site by the composite action between antibiotic templates and CuO, which led to the consistent adjustment of the imprinted sites and photoactive sites, thus enhancing the enzyme-like activity of TiO2 NRs/CuO/rMIP. In Addition, by adjusting the types and proportions of antibiotic templates during the preparation of MIP, TiO2 NRs/CuO/rMIP sensors with different response signals to four fluoroquinolones were prepared, and a sensor array was established based on them. Through an RGB analysis system of smart phone and PCA analysis method, qualitative and quantitative detection of the four fluoroquinolones was realized. The detection range of the four antibiotics was 0.1–3000 μM, which showed a good prospect for the actual detection of antibiotics.