Matrix-assisted pulsed laser deposition (PLD) allows a controlled layer-by-layer growth of polymer films. Di-octyl substituted polyfluorene (PF8) and its copolymers were deposited as thin films using matrix-assisted PLD by employing a KrF excimer laser with a fluence of 125 mJ/pulses. The optical and structural properties of these films are compared with spincoated films via Raman spectroscopy, absorption and photoluminescence. The Raman spectra of both PLD and spincoated films are similar indicating that the polymer films deposited via PLD maintain their molecular structure. Both the spincoated and the PLD grown PF8 films that were cast from toluene show the presence of the beta phase. Benzothiadiazole substituted PF8 (F8BT) and butyl phenyl-substituted PF8 (PFB) PLD grown films show a slightly broader emission compared to the spincoated films, which is attributed to an enhanced intermolecular interaction in the PLD grown thin films. (C) 2008 Elsevier B. V. All rights reserved.