Poly(L-lactide) (PLLA) and poly(L-lactide)/poly(ethylene glycol) (PLLA/PEG) electrospun fibrous materials coated with a polyelectrolyte complex (PEC) were prepared. This was achieved by consecutive deposition of a layer of N-carboxyethylchitosan (CECh) and a layer of a double hydrophilic block copolymer, poly(ethylene oxide)-b-quaternized poly[2-(dimethylamino)ethyl methacrylate] (PEO-b-PDMAEMAQ100), resulting in PEC formation between the two polyelectrolytes on the surface. Noteworthy, to improve the water wettability of the electrospun PLLA fibrous materials, that is, to enable more uniform deposition of the polyelectrolyte partners, water/ethanol mixed solvent was used for preparation of CECh and PEO-b-PDMAEMAQ100 solutions. The formation of PEC-based coating was demonstrated by means of scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The PEC formation allows targeted modification of the biological behavior of the electrospun materials as evidenced by the performed tests in respect to blood cells and pathogenic in microorganisms. In contrast to the pristine mats, the novel PEC-coated mats exhibit hemostatic properties and reduce the adhesion of pathogenic microorganisms