The bulky substituents of homosalen complexes decelerate the ring-opening polymerization of racemic lactide (LA). The substituent effects provide the first catalysis for the random copolymerization of epsilon-caprolactone (CL) with LA (CL/LA = 1:1). The copolymerization of CL with LA (CL/LA = 1:1) by the iPr(3)Si-substituted homosalen-Al complex 2 affords the practically random copolymer in a controlled manner. The reactivity ratios, average sequence lengths of CL and LA during the copolymerization, abundance ratios of the triad caproyl sequences, and T-g value of the obtained copolymer indicate that the copolymer was random with a somewhat alternative tendency (r(Cl/LA) = 0.80).