A novel solid-state electrochemiluminescence (ECL) quenching sensor based on the luminescent composite nanofibres for detection of bisphenol A (BPA) has been developed. The ruthenium(II) tris-(bipyridine) )-doped silica nanoparticles (Ru@SiO2) mixed the nylon 6 (PA6)/carboxylated multiwalled carbon nanotubes (MWCNTs) luminescent composite nanofibres (Ru@SiO2-MWCNTs-PA6) were successfully fabricated by a one-step electrospinning technique. The Ru@SiO2-MWCNTs-PA6 nanofibres, with unique 3D nanostructure, large specific surface area and double -ECL signal amplification, exhibited excellent ECL photoelectric behaviours on glassy carbon electrode. As a solid-state ECL sensor, the Ru@SiO2-MWCNTs-PA6 nanofibres can sensitively detect low concentration BPA by monitoring the BPA-dependent ECL intensity change. The detection limit for BPA is 2.28x10(-9)gL(-1), which is comparable or better than that in the reported assays. The sensor was successfully applied to determine BPA leached from real plastic samples with good recovery, ranging from 97.5% to 103.4%. The solid-state ECL sensor displayed wide linear range, high sensitivity and good stability. It holds promise for the electrospun nanofibre-based ECL sensors which have a great potential for routine analyses.