Glycerol carbonate (GLC) was synthesized from glycerol and dimethyl carbonate (DMC) over sodium aluminate (NaAlO) catalysts. The catalysts were prepared using a spray-drying method and compared with those prepared using the conventional hot-air drying method. Polyvinylpyrrolidone and glycerol were used as a catalyst template to increase the surface area and porosity of the catalysts. Additionally, different operating conditions were investigated such as the catalyst concentration, glycerol-to-DMC ratio, reaction temperature, reaction time, and catalyst reusability. The NaAlO catalyst prepared using the spray-drying method with 30 wt % glycerol as the template yielded the maximum GLC (85%) with 100% GLC selectivity.