Coumarin residues were conjugated to poly(vinyl alcohol) (PVA) by reacting epoxypropoxy coumarin (EPC) with the polymer. According to the peak areas on the 1H NMR spectrum, EPC was calculated to be conjugated to every 283 repeating units (vinyl alcohols). A cyclic photo-dimerization and dedimerization of EPC of PVA-EPC conjugate were observed under a cyclic irradiation of 365 nm and 254 nm. The salting-out of the conjugate significantly took a place in the range of 0-2.0M NaCl, and the phenomenon was observed at a lower concentration than that of unmodified PVA was. Oil-in-water emulsion was prepared as a template for the preparation of hollow microcapsules using chloroform as an oil phase and PVA-EPC as an emulsifier. The emulsion was stable for 24 hr in terms of droplet size. The wall surrounding droplets was built-up by the salting-out of PVA-EPC, and it was cross-linked by the irradiation of 365 nm. After chloroform was evaporated and salt was removed by a dialysis, hollow microcapsules were successfully obtained.