A highly chemoselective transesterification of methyl (meth)acrylates catalyzed by sterically demanding 2,6-di-tertbutyl-4-methylphenol (BHT)-derived NaOAr or Mg(OAr)2 was developed. The desired transesterification proceeded without undesired Michael additions under mild reaction conditions at 25 °C, and various primary and secondary alcohols, diols, triol, and tetraol on a scale of up to 10 mmol could provide the corresponding functionalized acrylates in high yields. Transition states were proposed based on monomeric and dimeric active species, and computational DFT calculations strongly supported the high chemoselectivity to minimize undesired Michael additions.