Cyclobutanetetracarboxylic dianhydride (CBDA) was prepared by photodimerization of maleic anhydride in capillary microreactors within Taylor flow under UV irradiation. Both inert gas and ultrasound were introduced into this photochemical process to avoid the potential channel clogging resulting from the CBDA deposition. Higher input power of the Hg lamp, lower reactant concentration, longer residence time, and smaller inner diameter of the capillary were found to result in higher CBDA yield. The yield of CBDA could reach as high as 66.3% at an actual residence time of 30 min in the capillary microreactor with 0.5 mm inner diameter. According to the analysis of energy conversion, only low effective photoelectric transformation efficiencies could be achieved in this photochemical process. However, the photonic efficiency for this photodimerization carried out in capillary photomicroreactors was much higher compared to batch photoreactors and was comparable with that for other photochemical transformations using similar photomicroreactors and light sources.