Using full atomistic classical molecular dynamics simulations, the interfacial properties of free-standing poly(3-hexylthiophene) (P3HT) films have been investigated. The orientations of different parts of the P3HT chain and the surface tensions of the films were calculated in a temperature range of 540 K–600 K. At the liquid/vacuum interface, the P3HT chain shows ordering by exposing hexyl groups at the interface, while the chain backbone lays flat with the thiophene ring preferentially tilt toward the surface. At the interface, the terminal methyl groups of hexyl side chains are in excess compared to the methylene groups or thiophene rings. The surface tension of P3HT in its melt state shows similar temperature dependence to that of polymers that have long alkyl side chains. The surface tension values are comparable to those polymers that expose methyl or methylene groups on the surface. The surface tension values determined for the melt state are lower than the experimental reported values for crystalline P3HT films, as expected.