An intense and broadband photoluminescence emission is demonstrated in a biocompatible film produced by thermal annealing of poly(acrylic acid) (PAA). The annealing process enhances the emission intensity from weakly emitting sub-luminophores of C–O and C=O functional groups by a factor of more than two orders of magnitude. The emission property can be sensitively tuned by the annealing temperature, duration, the PAA solution preparation conditions such as solvent type and solvent:PAA ratio. The strong luminescence is attributed to the formation of rigid molecular structure due to aggregation and crosslinking. FTIR measurements show that the aggregation and crosslinking processes subdue nonradiative recombination pathways.