Photolysis of microdroplets, stabilized by aminoquinoline-derived photosensitive surfactants composed of polyethyleneglycol/perfluorinated polyether (PEG/PFPE) diblock amphiphiles by using 355 nm ps pulsed laser light, resulted in rapid controlled coalescence of targeted microdroplets offering the prospect of a novel type of droplet merging with high stereospatial integrity for microfluidic systems.