We have investigated the initial stages of vacuum-deposited sexithiophene (α-6T) adlayer formation on Au(111) vicinal surfaces at room temperature. The in situ scanning tunneling microscopy (STM) and photoemissionspectroscopy (PES) reveal a step edge-driven growth of α-6T on the Au(111) vicinal surfaces that first leadsto the formation of an ordered monolayer, comprising two phases with the molecular major axes alignedalong the step edges. The monolayer formation is then followed by the appearance of a single-phase 2Dsuperstructure at a two-monolayer coverage. The results highlight the potential of using vicinal metal surfacesas templates for generating organized organic nanostructures over macroscopic areas for applications in organicelectronics and moletronics.