A series of Al(III) unsymmetrical beta-aminoalcohol based complexes 1-6 were synthesized via metalation of the corresponding ligands 1'-6' those were prepared by the reaction of benzylamine with readily available epoxides viz., styrene oxide, 1,2-epoxy-3-phenoxypropane, 4-tertbutylphenyl glycidyl ether, 4-chiorophenyl glycidyl ether, glycidyl 2-methylphenyl ether and 1,2-epoxyhexane. Among these complexes, the complex 2 was found to be most effective in the cycloaddition of aryloxy/aliphatic terminal epoxides with CO2 under atmospheric pressure to get corresponding cyclic carbonates with high conversion and selectivity (up to >99%) in the presence of tetrabutylammonium bromide as a co-catalyst. The DFT calculations revealed the important role played by counter-ion in the co-catalyst during cycloaddition reaction of CO2 with the substituted epoxides. (C) 2016 Elsevier B.V. All rights reserved.