Whilst being thoroughly used in the textile industry and biomedical sector, silk has not yet been exploited for fibre optics-based sensing although silk fibres directly obtained from spiders can guide light and have shown early promises to being sensitive to some solvents. In this communication, a pioneering optical fibre sensor based on spider silk is reported, demonstrating for the first time the use of spider silk as an optical fibre sensor to detect polar solvents such as water, ammonia and acetic acid.