Interfaces bearing firmly attached thiol groups are useful for many applications requiring the versatile and facile chemistry of the -SH functionality. In this work， rugged ultrathin films were prepared on substrates using layer-by-layer assembly. The surface of these smooth films was capped with a co-polymer containing benzyl mercaptan units. The utility of this coating was illustrated by three applications. First， thiol-ene "click" chemistry was used to introduce the Arg-Gly-Asp (RGD) adhesive peptide sequence on a surface that otherwise resisted good adhesion of fibroblasts. This treatment promoted cell adhesion and spreading. Similar Michael addition chemistry was employed to attach poly(ethylene glycol) to the surface， which reduced fouling by (adhesion of) serum albumin. Finally， the affinity of gold for -SH was exploited by depositing a layer of gold nanoparticles on the thiolated surface or by evaporating a tenacious film of gold without using the classical chromium "primer" layer.