A stable high-temperature reaction site and the uniformity and speed of heating the feedstocks play a key role in pyrolysis processes. In this study, microwave-assisted heating coupled with atomization feeding was used to pyrolyze methyl ricinoleate (MR) for the efficient, continuous production of undecylenic acid methyl ester (UAME) and heptanal (HEP). The effects of feed mode, reaction temperature and preheating temperature on microwave-assisted pyrolysis (MAP) were examined. The maximum selectivities of HEP and UAME could reach 91.4 wt.% and 76.6 wt.%, respectively, at the reaction and preheating temperatures of 500 °C and 150 °C, respectively, using atomization feeding. The gas, liquid and solid products were determined by gas chromatography (GC), GC-mass spectrometry (MS) and Fourier transform infrared (FT-IR), and the gas, liquid and solid yield reached 7.0 wt.%, 89.0 wt.% and 0.1% wt.%, respectively, with an error of 3.9 wt.% at 500 °C. The pyrolysis of MR via microwave-assisted heating coupled with atomization feeding was found to be more efficient than the conventional pyrolysis process. In addition, the theoretical and actual heat for MAP of MR was 1461 kJ/kg and 2629 kJ/kg at 500 °C, respectively. The material balance and heat analysis results can be used to guide the design of an amplifying device.