This paper describes recent advances in the development of bioelectrochemistry research which is focused on the advanced design and preparation of enzyme-based amperometric biosensors, as well as the functional structure and principle. Particular emphasis is directed to the discussion and exploration of electrochemical biosensors based on novel functional polymer, polymaleimidostyrene (PMS), as effective immobilization support and stabilizer. The sulphydryl and amino groups of enzymes react with maleimide groups of PMS. As a result, various enzymes can be easily modified on the electrode surface. First topic is PMS-based enzyme-micelles which are dispersed in the polystyrene film prepared on the electrode surface. The structure and morphology of enzyme-micelles membranes were characterized by scanning electron microscope. Second topic is bio-functionalization of electrode surface using enzyme-immobilized PMS. Electrochemical and bioelectrocatalytic properties of enzyme-micelle membranes were examined by various electrochemical techniques. These enzyme-micelle-based electrochemical biosensors exhibited good sensitivity and selectivity for the detections of urea, uric acid, L-ascorbic acid, glucose and toxic phenol compounds. The prospects and further developments in this exciting interdisciplinary field are also suggested.