Nowadays, microwave heating has evolved into a common tool for chemists based on its numerous advantages over conventional conductive heating. Surprisingly, the efficiency of microwave-assisted heating is still rather unexplored. In this contribution, we report our investigations concerning the heating efficiency of a variety of solvents including polar and apolar substances. Moreover, the effects of adding salt or passive heating elements on the microwave heating efficiency will be addressed. Finally, the heating efficiency of demineralized water is discussed at different volumes and with different microwave power levels in both monomode and multimode microwave synthesizers, demonstrating maximum average heating efficiencies of 10% for small-scale vessels (5 mL), 20% for medium-scale (50 mL), and 30% for large-scale microwave heating (400 mL). © 2009 CSIRO.