13,6-N-Sulfinylacetamidopentacene (SAP) has been transferred on solid substrates both by water-rich environment and organic solvents without altering his chemical structure. Thermal conversion of SAP to pentacene leads to crystals showing similar features of vacuum-sublimated pentacene both in the bulk and thin-film phases. The thin-film phase is strongly affected by the substrate surface properties. Low energy Si–CH3 rich surfaces allow for the formation of compact micrometric crystals following a Volmer–Weber like growth with orientation suitable for field-effect carrier mobility. Screw dislocations along with straight edges are found on these systems as an indication of a loose interlayer interaction with respect to the lateral π–π intermolecular forces. In contrast, higher energy SiOH rich surfaces result in non-compact systems (Stransky–Krastanov like growth) arising by in-space randomly oriented crystals as …