Polystyrene (PS), poly(methyl methacrylate), poly(vinyl acetate), and 1,2-poly(1,3-butadiene) were labeled with naphthyl groups using a focused UV lamp irradiation technique. Photolabelings of PS with anthracene, fluorene, and phenanthrene chromophores were also readily achieved. Fast labeling rates and high labeling efficiency (greater-than-or-equal-to 40 labels per PS chain) were achieved when PS was irradiated in the presence of 9-bromofluorene or 9-bromophenanthrene. No significant molecular-weight changes were observed in the PS photolabeling systems. The fluorescent labels attached to the PS chain were characterized by spectroscopic analysis.