Several heterogeneous catalysts have been investigated for solvent-free synthesis of propylene carbonate (PC) for cycloaddition reaction of propylene oxide (PO) and carbon dioxide (CO2). The characterization of different heterogeneous catalysts has been successfully carried out using Raman spectroscopy, scanning electron microscopy, and X-ray diffraction analysis. Batch cycloaddition reaction of PC and CO2 has been conducted in a high pressure reactor. The effect of various parameters that could influence the conversion of PO and the selectivity and yield of PC such as catalyst types, catalyst loading, CO2 pressure, reaction temperature, and reaction time has been studied to find the optimum conditions and the best preferred catalyst for this reaction. Ceria and lanthana doped zirconia (Ce–La–Zr–O) catalyst has been found to be the most active and selective for synthesis of PC as compared to other heterogeneous catalysts that were tested as part of this research. Catalyst reusability studies have been conducted to investigate the long-term stability of the best performed catalyst for synthesis of PC, and it has been found that the catalyst could be reused several times without losing its catalytic activity. An artificial neural network (ANN) model has been developed for PC synthesis by cycloaddition reaction of PO and CO2 using Ce–La–Zr–O catalyst to compare the experimental data and the predicted results by ANN model. The ANN model predicted values are in good agreement with the experimental results.