An efficient geometrical E→Z isomerisation of vinyl silanes is disclosed via selective energy transfer using an inexpensive organic sensitiser. Characterised by operational simplicity, short reaction times (2 h), and broad substrate tolerance the reaction displays high selectivity for trisubstituted systems (Z:E up to 95:5). In contrast to thermal activation, directionality results from deconjugation of the π-system in the Z-isomer due to A1,3-strain thereby inhibiting re-activation. The structural importance of the β-substituent logically prompted an investigation of mixed bis-nucleophiles (Si, Sn, B). These versatile linchpins also undergo facile isomerisation, thereby enabling a formal anti-metallometallation. Mechanistic interrogation, supported by a theoretical investigation, is disclosed together with application of the products to the stereospecific synthesis of biologically relevant target structures.