Aqueous mixtures of hyaluronic acid and poly(vinyl alcohol) system and hydrogels thereof were introduced to obtain new bioartificial materials that have excellent mechanical properties, biocompatibility and enhanced rheological properties. The interactions between hyaluronic acid and poly(vinyl alcohol) and/or borax were investigated by rheological measurements. Preparation parameters of the aqueous mixtures were mixture composition, the degree of hydrolysis of poly(vinyl alcohol) and borax concentration. From the rheological behavior, it could be deduced that the key factor of the interaction between hyaluronic acid and poly(vinyl alcohol) was the hydrogen bonding between them and the effect was pronounced with borax. Enhanced viscosity was observed at the composition of $20wt\%$ of hyaluronic acid solution and $80wt\%$ of poly(vinyl alcohol) and borax solution. Rheological properties were influenced by the degree of hydrolysis of poly(vinyl alcohol) and borax concentration. As the degree of hydrolysis and borax concentration increased, rheological properties increased due to the increased hydrogen bonding and networking of hyaluronate aggregates. Physical hydrogels from hyaluronic acid and poly(vinyl alcohol) were prepared and the composition dependence of the gels was rheologically investigated as well.