In this study, we present the synthesis and characterisation of Ce-doped ZnO nanostructures utilizing the SILAR approach. The effect of Ce-doping on the structure, optical, electrical, and photocatalytic activity of ZnO nanoflowers was investigated in detail. Microscope images confirmed that the ZnO nanoparticles had a nanoflower-like shape. Mapping analysis confirmed that the Ce ions were uniformly distributed in the ZnO matrix. The incorporation of Ce influenced the material's surface features, leading to an increase in surface roughness. The diffraction result showed that the size of the crystals increased from 57.3 to 60.3 nm with 5.0 % Ce-doping. The FTIR spectra of the samples showed the Ce–O bonds in the region of 510–1000 cm−1. Systematic reduction of the band gap from 3.24 to 3.05 eV was observed with increasing concentration of Ce from 0.0 to 5.0 %. It was also found that the surface roughness also affected the electrical properties and increased the specific contact resistance with Ce doping. Furthermore, the photocatalytic activity of the nanoparticles was also investigated for the degradation of methylene blue under UV-light irradiation. The turnover number and turnover frequency were also determined to rank the catalytic activity of the fabricated nanoparticles. The results indicated that 3.0 % Ce-doping enhanced the photocatalytic activity and degraded 95.8 % MB within 120 min. These findings indicate that cerium-doped ZnO shows great potential as an effective material for environmental purification processes.