Recently, there has been great interest in the application of polysaccharides in the preparation of diverse biomaterials which result from their biocompatibility, biodegradability and biological activity. In this work, the investigations on chitosan/poly(aspartic acid)-based hydrogels modified with starch were described. Firstly, a series of hydrogel matrices was prepared and investigated to characterize their swelling properties, structure via FT-IR spectroscopy, elasticity and tensile strength using the Brookfield texture analyzer as well as their impact on simulated physiological liquids. Hydrogels consisting of chitosan and poly(aspartic acid) in a 2:1 volume ratio were elastic (9% elongation), did not degrade after 30-day incubation in simulated physiological liquids, exhibited a relative biocompatibility towards these liquids and similar swelling in each absorbed medium. This hydrogel matrix was modified with starch wherein two of its form were applied—a solution obtained at an elevated temperature and a suspension obtained at room temperature. Hydrogels modified with hot starch solution showed higher sorption that unmodified materials. This was probably due to the higher starch inclusion (i.e., a larger number of hydrophilic groups able to interact with the adsorbed liquid) when this polysaccharide was given in the form of a hot solution. Hydrogels modified with a cold starch suspension had visible heterogeneous inequalities on their surfaces and this modification led to the obtainment materials with unrepeatable structures which made the analysis of their properties difficult and may have led to misleading conclusions.