Coplanar electrodes formed from asymmetric metals separated on the nanometre length scale are essential elements of nanoscale photonic and electronic devices. Existing fabrication methods typically involve electron-beam lithography—a technique that enables high fidelity patterning but suffers from significant limitations in terms of low throughput, poor scalability to large areas and restrictive choice of substrate and electrode materials. Here, we describe a versatile method for the rapid fabrication of asymmetric nanogap electrodes that exploits the ability of selected self-assembled monolayers to attach conformally to a prepatterned metal layer and thereby weaken adhesion to a subsequently deposited metal film. The method may be carried out under ambient conditions using simple equipment and a minimum of processing steps, enabling the rapid fabrication of nanogap electrodes and optoelectronic devices with aspect ratios in excess of 100,000.