In this work, optimized conditions for preparation of chitosan and hyaluronan polyelectrolyte complex are proposed. The objective was to produce new biomaterials being biocompatible and bioresorbable in the body as well as approaching the extracellular matrix (ECM) structure. These materials will be tested for chondrocyte development in tissue engineering and wound healing applications. Nanofibers made of the polyelectrolyte complex (PEC) were successfully manufactured by electrospinning, and casted films were used as a model for properties comparison. To our knowledge, it is the first time that stable chitosan/hyaluronan fibers are produced, which were observed to be long-lasting in buffer at pH~7.4. The role of thermal treatment at 120 • C for 4 h is examined to control the degree of swelling by crosslinking of the two polysaccharides by H-bonds and amide bonds formation. The properties of the materials are tested for different PEC compositions at different pH values, based on swelling and solubility degrees, diameters of nanofibers and mechanical performances. The influence of the solvent (acidic potential and composition) utilized to process biomaterials is also examined. Acid formic/water 50/50 v/v is observed to be the more appropriated solvent for the carried-out procedures.