The granular macro-reticular water-insoluble polyvinyl alcohol was prepared directly from PVA with terephthaldehyde as crosslinking agent and ethylene glycol or teteraethy-lene glycol as diluent via water in oil type suspension system. It has been acetylized or esterified to obtain tertiary amine group or carboxy group containing functional carriers. The carboxy group containing carriers would react further with N-hydroxysuccinimide to give the active ester which would conjugate effectively with protein or enzyme under mild condition.