Template stripping of An films in ultrahigh vacuum (UHV) produces atomically flat and pristine surfaces that serve as substrates for highly ordered self-assembled monolayer (SAM) formation. Atomic resolution scanning tunneling microscopy of template-stripped (TS) Au stripped in UHV confirms that the stripping process produces a flat, predominantly < 111 > textured, atomically clean surface. Octanethiol SAMs vapor deposited in situ onto UHV TS Au show a c(4 x 2) superlattice with (root 3 x root 3)R30 degrees basic molecular structure having an ordered domain size up to 100 nm wide. These UHV results validate the TS Au surface as a simple, clean and high-quality surface preparation method for SAMs deposited from both vapor phase and solution phase.