Thin films of head-tail (H-T) regio-regular poly[3-(4-octyloxyphenyl) thiophene] (POOPT) were grown using the MAPLE (Matrix Assisted Pulsed Laser Evaporation) technique in which the target is a frozen solution of the polymer in chloroform. Target evaporation was obtained by laser irradiation at 1064 nm and substrates were kept at different temperatures. Information concerning the preservation of the polymer local chemical structure following laser irradiation was obtained by FTIR (Fourier Transform InfraRed) spectroscopy. Based on FTIR data, the chemical structure of the deposited polymer seemed to undergo little or no damage. From UV-Visible spectroscopic analysis, it turned out that the degree of order of the film is strongly affected by the substrate temperature: the polymer was deposited in a disordered form on the substrate at room temperature whereas on the hot surface we locally obtained the π-stacked structure characteristic of polythiophenes. Atomic force microscopy (AFM) images showed that the polymer formed aggregates of different dimensions (<1 μm to 5 μm) with a columnar shape and showed micrometric domains with sharp and apparently regular edges for the film grown on a hot substrate. Electrical measurements performed by a standard two-probe technique confirm that the structural order degree strongly affects the film charge transport properties.