AbstractIn this paper, a novel hierarchically structured ZnO photoanode for use in quasi‐solid state dye‐sensitized solar cells (DSCs) is presented. The film is composed of polydisperse spindle‐shaped ZnO particles that are prepared through direct precipitation of zinc acetate in aqueous solution. Without additional pore‐forming agents, the microporous structure is well constructed through the packing of polydisperse ZnO particles. In the film, small ZnO particles are able to improve interparticle connectivity and offer a large internal surface area for sufficient dye‐adsorption; on the other hand, particles of larger size can enhance the occurrence of light‐scattering and introduce micropores for the permeation of quasi‐solid state electrolytes. Meanwhile, morphologies, particle size, and specific areas of the products are controlled by altering the reactant concentration and synthetic temperature. Combined with a highly viscous polymer gel electrolyte, a device based on this ZnO photoanode shows high conversion efficiencies, 4.0% and 7.0%, under 100 and 30 mW cm−2 illumination, respectively. Finally, the unsealed device is demonstrated to remain above 90% of its initial conversion efficiency after 7 days, showing excellent stability.