In this study, Z-scheme 0D/1D BiVO4/CdS nanostructure was successfully prepared with outstanding performance toward photocatalytic enrofloxacin (ENR) removal process. The best performance was gained on BVO/CdS-2 sample (k = 0.0313 min−1), which was 3.3 and 8.7 times higher than that of pure CdS and BiVO4 samples, respectively. The obtained dot-on-rod architecture exhibited improved separation efficiency of photo-excited electron-hole pairs owing to the rapid transfer of charge carriers. The Z-scheme transfer was also confirmed via electron spinning resonance (ESR) analysis with the generation of both·OH and·O2-. This paper could supply new insights into the fabrication of Z-scheme nanostructure with highly efficient toward photocatalytic environmental remediation.