This work reported a novel poly(lactic-co-glycolic acid) (PLGA) composite nanofibres, Chitosan-graft-PLGA (CS-graft-PLGA), produced by the electrospinning technique. CS was grafted onto the PLGA surface via the cross-linking agents reacting with the PLGA with reactive carboxyl groups on its surfaces introduced from the alkali treatment. The CS grafting ratios of the electrospun CS-graft-PLGA nanofibres were about 2.43%, 4.34%, 16.97% and 39.4% after cross-linked for 12 h, 16 h, 20 h and 24 h, respectively. The electrospun CS-graft-PLGA nanofibres were significantly uniform and highly smooth without the occurrence of bead defects, even at high CS grafting ratio. The electrospun CS-graft-PLGA nanofibres not only possessed the improved hydrophilicity and the protein absorption property, but also maintained the good mechanical property. In addition, the CS grafting can be conducive to accelerate degradation rate of PLGA.