The paper describes the effect of different thermal treatments on the morphology and binding properties of particles prepared using a transacylation reaction between two biocompatible polymers, namely propylene glycol alginate and human serum albumin. Compared to control alginate gel microspheres, albumin–alginate covalent network offers a better resistance to the microspheres towards freezing, lyophilization and sterilization. The binding properties for methylene blue were not altered by the treatments. Moreover, stability in physiological environments opens interesting applications in biological and pharmaceutical fields.