We report on the simple, in situ generation of CdS nanocrystals inside electrospun polymer fibres by thermal decomposition of a cadmium thiolate precursor, leading to nanocomposite light-emitting fibres. The modifications induced in the precursor by the thermal decomposition are investigated by a morphological, structural and spectroscopic analysis of the resulting nanocomposite fibres. This approach allows us to overcome nanofabrication difficulties related to disfavoured micro- or nanofluidic molecular flow as given by the direct incorporation of particles in the electrospinning solution. This method therefore enables the synthesis of luminescent, CdS-based composite fibres with emission peaked in the visible range, suitable as building blocks for nanophotonic devices based on light-emitting nanomaterials.