ZnO nanowire (NW)-layered basic zinc acetate (LBZA)/ZnO nanoparticle (NP) composite electrodes with different NP occupying extents have been synthesized using a simple wet-chemical route for use in dye-sensitized solar cells (DSSCs). By employing mercurochrome as the sensitizer, superior efficiencies (η) of 1.27–2.37% are obtained using the ZnO NW-LBZA/ZnO NP composite electrodes composed of a 5.5 µm thick NW array with different NP occupying extents in comparison with the ZnO NW DSSC (η = 0.45%). It suggests that the ZnO NW-LBZA/ZnO NP composite films which possess a considerable enlarged surface area by NPs growth, without sacrificing electron transport efficiency of single-crystalline ZnO NWs at the same time, are promising photoanodes for use in DSSCs. In addition to the extent of NP occupation, the overall efficiency of the ZnO NW-LBZA/ZnO NP composite DSSC is also influenced by the thickness of the composite film as well as the LBZA fraction and the cracks within the composite. The fraction of LBZA affected by the NP growth period and post-annealing conditions is found to play a crucial role in electron transport through the composite anode. Up to now, a high efficiency DSSC of 3.2% is achieved using a mercurochrome-sensitized and 6.2 µm thick NW–NP composite film.