The influence of ultraviolet (UV) light irradiation on the emulsification properties of mixtures of an anionic surfactant, sodium dodecyl sulfate (SDS), and a photoresponsive cationic surfactant, 2-(4-(4-butylphenyl)diazenylphenoxy)ethyltrimethylammonium bromide (C4AzoTAB), containing an azobenzene group has been investigated. When mixtures of n-octane and aqueous SDS/trans-C4AzoTAB solution are homogenized, stable emulsions are obtained in regions of specific surfactant concentrations and molar ratios of the mixed surfactants. The stable emulsions are stable for over a week and found to be of the oil-in-water (O/W) type. UV light irradiation of the stable O/W emulsions leads to the coalescence of smaller oil droplets into larger ones in the emulsions, i.e., demulsification. As a result, the oil and aqueous surfactant solution phases are fully separated by UV light irradiation for 90 min, even shorter than our previous result (6 h; Langmuir 2014, 30, 41-47). The use of a microreactor shortens the time required for the photoinduced demulsification into 3.5 min. When mixtures of octane and aqueous SDS/cis-C4AzoTAB solution are homogenized, no emulsions are obtained. The interfacial tension (IFT) between octane and aqueous SDS/cis-C4AzoTAB solution is higher than that between octane and aqueous SDS/trans-C4AzoTAB solution, indicating that the IFT of SDS/trans-C4AzoTAB mixtures increases with the cis photoisomerization of the trans isomer. These results suggest that cis isomerization of the SDS/trans-C4AzoTAB mixtures due to UV light irradiation causes Ostwald ripening of the octane droplets in the emulsions, thereby reducing the interfacial area between the octane and water phases as the IFT between octane and the aqueous surfactant solution increases. Subsequently, the octane and aqueous solution phases separate.