Abstract: Using chloromethyl polystyrene resin as matrix, a new macroporous adsorption resin of immobilized black wattle tannins(MARIT) was prepared through Mannich reaction. The condition of reaction was determined by means of orthognonal experiment. Equilibrium data for the adsorption of phenol from aqueous solution by macroporous adsorption resin as adsorbent had been obtained which were correlated with Freundlich isotherm equation. Isosteric adsorption enthalpy, adsorption free energy and adsorption entropy were calculated according to the relationship of thermodynamic function. Isosteric adsorption enthalpy was 8.95-13.41 kJ/mol, which reveals a hydrogen-bonding adsorption mechanism. Difference of adsorption properties of phenol onto MARIT from aqueous solution and cyclohexane solution, as well as difference of adsorptions of phenol, resorcinol and o-nitrophenol from aqueous solution were studied, and the results further demonstrated the hydrogen-bonding based adsorption for phenol from non-aqueous solution.