Aluminum trichloride (AlCl3) catalyzed copolymerization of polar monomers, including both methyl methacrylate (MMA) and methyl acrylate (MA), with nonpolar 1-octene is investigated. The copolymerization of MMA and 1-octene produces copolymers with acceptable productivity in the present of AlCl3, but no alternating copolymer can be obtained even in a 1-octene rich condition (n(1-octene)/n(MMA) = 6.14/1). However, AlCl3-catalyzed copolymerization of MA and 1-octene unveils that MA is more feasible than MMA to copolymerize with 1-octene for the formation of alternating copolymer. An alternating copolymer of MA and 1-octene can be obtained even at MA-rich conditions (n(1-octene)/n(MA) = 0.58/1). Meanwhile, temperature shows a significant impact on the copolymerization behaviors. Performing AlCl3-catalyzed copolymerization of MA and 1-octene at lower temperature leads to an increase in the molecular weight and the incorporation of MA into the backbone of the copolymer, probably due to low temperature-enhanced complexation between AlCl3 and the ester functionality.