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