A novel concept for the synthesis of a stable polymer hybrid matrix bead was developed in this study. The beads were further applied for enzyme immobilization to produce stable and active biocatalysts with low enzyme leakage, and high immobilization efficiency, enzyme activity, and recyclability. The immobilization conditions, including PEI concentration, activation time and pH of the PEI solution were investigated and optimized. All formulated beads were characterized for its functionalized groups, composition, surface morphology and thermal stability. Compared with the free beta-glucosidase, the immobilized beta-glucosidase on the hybrid matrix bead was able to tolerate broader range of pH values and higher reaction temperature up to 60 degrees C. The immobilized beta-glucosidase was then used to hydrolyse pretreated macroalgae cellulosic residue (MCR) for the production of reducing sugar and a hydrolysis yield of 73.4% was obtained. After repeated twelve runs, immobilized beta-glucosidase retained about 75% of its initial activity. (C) 2015 Published by Elsevier Ltd.