This study explores the molecularly templated reaction of pyrene-terminated telechelic poly(dimethyl siloxane) (PDMS) with graphene oxide (GO) to produce composite elastomers. These materials undergo chemical crosslinking between secondary amides near PDMS chain ends and epoxies on the surface of GO as confirmed by infrared spectroscopy, rheology, gel content, and mechanical property measurements. The incorporation of pyrene end groups introduces pi-pi interactions with GO surfaces that enhance the reaction efficacy of the nearby secondary amide groups. As a comparison, methoxy-terminated telechelic PDMS containing the same secondary amides near the chain ends did not exhibit appreciable crosslinking with GO. Depending on the concentration of the amide groups, the pyrene-terminated PDMS/GO elastomer can be highly crosslinked (e.g., up to 96 wt % gel) but highly extensible (e.g., extensional strains of more than 200%). This general strategy could be implemented using other amide containing polymers to produce a wide range of high-performance thermosets and elastomers. (C) 2017 Wiley Periodicals, Inc.