presented herein is the organic synthesis and thin film (tf) assembly of six alkyl-substituted thiocyante and selenocyante bithiophene molecules: ncse-t2-hx, ncs-t2-hx, ncs-hx-t2-hx, ncse- hx-t2-hx, ncs-hx-t2-hx-scn and ncse-hx-t2-hx-secn. tfs assembled from these thio and selenocyanates were characterized by six different techniques: electrochemical capacitance (cp) measurements, scanning electron microscopy (sem), energy dispersive x-ray spectroscopy (edx), atomic force microscopy (afm), x-ray photoelectron spectroscopy (xps) and time-of-flight secondary ion mass spectrometry (tof-sims). cp experiments were used to confirm the development of tfs on an amorphous au surface using ethanol or hexanes as a reaction solvent. a sputtered au surface was observed by sem/edx to be an inappropriate surface for tf assembly. tfs assembled onto epitaxially grown au were characterized by multiple techniques. large crystallites were observed on tfs assembled from ncse-t2-hx and ncse-hx-t2-hx-secn. chemical maps of these crystallites were obtained through sem/edx. the presence of a covalent au-s or au-se bond on the surface was confirmed by xps signals from the s 2p3/2 and se 3d5/2/3d3/2 regions respectively. xps signals of ~ 399 ev in the n 1s region were observed in all assemblies characterized by this technique, indicating the presence of residual gold-bound cyanide (au(cn)ads) on the surface. tof-sims chemical intensity maps confirmed the presence of expected tf fragments on the surface of all tfs characterized by this technique. tof-sims results suggested that tfs connected to the au surface through an aromatically bound s or se atom produced tfs with higher surface coverage.