Fibrous poly(L-lactide) (PLLA) and bicomponent PLLA/poly(ethylene glycol) mats were prepared by electrospinning and then were coated with chitosan. The presence of chitosan coating was proved by scanning electron microscopy and by fluorescence microscopy. On contact with blood, the chitosan coating led to changes in erythrocyte shape and in their aggregation. The haemostatic activity of the mats increased with increasing chitosan content. Microbiological studies against Staphylococcus aureus revealed that the chitosan coating imparts antibacterial activity to the hybrid mats. The combined haemostatic and antibacterial activities render these novel materials suitable for wound-healing applications.