Heterogeneous catalysts are preferred in fine chemical industries due to their easy recovery and reusability. Here, we report an easily scalable method of ZnO catalysts for coumarin synthesis. Nanocrystalline ZnO particles with diverse morphologies and crystallite sizes were prepared using different solvents. The change in morphology results in changes in band gaps, defects, basicity, and textural properties (surface areas, pore volumes, and pore sizes). The catalytic performances of the synthesized ZnO materials were tested using coumarin synthesis via the Knoevenagel condensation. The catalyst synthesized using methanol shows the highest activity and selectivity (conversion of 74%, selectivity of 94%) with a turnover number of 14.69. The increased activity of the ZnO synthesized in methanol is attributed to the combined effects of moderate basicity and relatively high textural properties of the sample.