The increasing demand for biodiesel (BD) as a renewable and sustainable energy source has impelled the generation of abundant and low-cost byproduct glycerol, which accounts for 10 wt% of total BD production and requires urgent utilization. The transesterification reaction, which utilizes glycerol and dimethyl carbonate (DMC) to synthesize valuable glycerol carbonate (GC) is an established reaction pathway to valorize oversupplied glycerol. Commercialization of inexpensive GC is constrained by the nature, stability, and basicity of applied catalyst, reaction conditions, types of the reactor system and separation methods of reaction products. This study presents a review and diversity of recent reports on reactor systems and DMC-methanol azeotrope separation strategies explored in GC synthesis from biodiesel-derived glycerol. Also, recent trends on heterogeneous catalysts, their performance, and the effects of reaction conditions were presented. Conducted studies revealed that the choice for reactor systems is constrained by factors such as energy consumption and operational safety and a significant mild reaction conditions could be realized using a microwave reactor. Furthermore, the reactive-extractive distillation and pervaporation processes showed high energy-efficiency and appreciable separation of DMC-methanol azeotrope. Thus, the development of stable catalyst and process intensification to fabricate an integrated reactor-separation system with high energy efficiency are fundamental and must be explored. This study portrays the recent research effort made in this direction and the limitations that require urgent attention.