A new electrochemical immunoassay strategy was proposed based on electrostatic interaction of natural polymers. The chitosan-entrapped carbon paste electrode (CCPE) was used as the base electrode, alginates as carriers for the reactants and horseradish peroxidase (HRP) as enzyme label in the immunoassay. The immunoassay was firstly carried out using the homogeneous competitive immune format and a very high rate of immune reaction was reached since both reacting antibodies and antigens were in a solution phase. Subsequently quick heterogeneous separation of immune complexes attached to the algi...