Polyelectrolyte complex diazoresin-poly(sodium styrene sulfonate) (DR-PSS) from diazoresin (DR) as cationic polyelctrolyte and poly(sodium styrene sulfonate) (PSS) as anionic polyelectrolyte does not dissolve in water or organic solvent because of its electrostatic crosslinking structure. It was found that the complex dissolves considerably aqueous solution of sodium dodecyl sulfate (SDS) and confirmed that the DR-PSS-SDS system possesses extraordinary thermostability as well as high photosensitivity and can be used directly to produce a photoimaging coating.