We present here the luminescent properties of microstructures obtained through femtosecond (fs) laser direct writing (LDW) in bulk, and thin films of polymers such as poly methyl methacrylate (PMMA), poly dimethyl siloxane (PDMS), polystyrene (PS), and poly vinyl alcohol (PVA). We report the transmission, emission, excitation, laser confocal and ESR data from the modified regions acquired with the intention of understanding the fs irradiation effects in these polymers. Formation of different optical centers in the laser irradiated regions has been identified as the reason for emission characteristics which are dependent on the excitation source. Such emitting microstructures demonstrate their utility in memory based devices. ESR studies reveal the existence of peroxide type free radicals in PMMA, PDMS and PS after fs laser irradiation. (C) 2010 Elsevier B. V. All rights reserved.