Four novel di-nuclear yttrium catalysts coordinated by bis(benzotriazole iminophenolate) (BiIBTP) ligands have been synthesized and structurally characterized. The one-pot procedure of BiIBTP pro-ligand with [Y(NO3)(3) center dot 6H(2)O] (1.0 equiv.) and 2-nitrophenol derivative (1.0 equiv.) in the presence of triethylamine (5.0 equiv.) under refluxing MeOH solution gave bimetallic yttrium nitrophenolate complexes 1-4, [(mu-BiIBTP)Y(L)](2) (BiIBTP = (C13C) BMIBTP or (C83C) BMIBTP; L =2-nitrophenolate or 2,4-dinitrophenolate) with good to high yields. The solid-state structure of 1 and 3-4 exhibits a di-yttrium(III) di-nitrophenolate species with the pentadentate BiIBTP ligand chelating two metal atoms. Versatile catalysis towards ring-opening polymerization of cyclic ester and copolymerization of internal epoxides with carbon dioxide (CO2) or phthalic anhydride (PA) catalyzed by these di-yttrium nitrophenolate complexes was systematically studied. Experimental results revealed that air-stable complexes 3 and 4 were shown to effectively catalyze not only lactide polymerization but also copolymerization of cyclohexene oxide (CHO) with CO2 or PA. Among these compounds, di-Y complex 4 was the most active catalyst for the ring-opening polymerization of L-lactide in combination with 9-anthracenemethanol, providing poly(L-lactide)s having the expected molecular weight and narrow molecular weight distribution. Furthermore, catalyst 3 was capable of copolymerizing CO2 and CHO in the presence of co-catalysts under mild conditions, producing perfectly alternating poly(cyclohexene carbonate)s with the controllable character. In addition, the molecular weight controllable poly(PA-co-CHO)s with high ester linkage contents could be afforded on copolymerizing PA and CHO utilizing di-yttrium complex 3 as the catalyst. This work provides the facilely synthesized di-nuclear yttrium complexes as versatile catalysts for three different types of polymerization catalysis.