The demand for green energy derived from plant feedstock has been the determining factor for the abundant supply of glycerol. Concerted efforts have been made to expand the current scope of glycerol application. This study describes the rapid polymerisation of crude glycerol directly obtained from the biodiesel process to produce polyglycerol via microwave heating technology. Crude glycerol used in this study was obtained from four different biodiesel pilot plants. Commercially pure glycerol was used as the control in all the parameters studied. The highest percent yield of polyglycerol obtained was 94.94% when heated at 250oC for 60 min under microwave irradiation. Crude glycerol that gave the highest polyglycerol percentage was found to contain the highest percent of soap (12.5%). It was anticipated that a high conversion of glycerol was due to the soap contained in the crude glycerol. This study showed that biodiesel-based crude glycerol with appropriate soap content could be used directly as a raw material in polyglycerol production.