Recent advances on protem-polysaccharide electrostatic complex and coacervates' formation, structure and properties are presented. The first section emphasises on the thermodynamics of complexes formation, the contribution of enthalpic and entropic effects is specifically discussed. Then, their structure is described at different length scales and recent findings on the phase-ordering dynamics of complex and coacervates formation are covered. Finally, the most relevant functional properties of protein-polysaccharide complexes and coacervates for food applications are described. (C) 2007 Elsevier Ltd. All rights reserved.