The optimization of the synthesis of homopolymers from n-butyl acrylate (BA), styrene (Sty), and methyl methacrylate (MMA), using copper-based atom transfer radical polymerization (ATRP) with tris(2-dimethylaminoethyl)amine (Me-6-TREN) as a ligand is reported. Catalyst concentration (copper bromide complexed with 1 equiv of Me-6-TREN) as low as 1% relative to initiator (50 ppm in the reaction mixture) was sufficient to successfully prepare well-defined poly(n-butyl acrylate) in bulk. With 50% catalyst to initiator, styrene was polymerized in bulk. The deactivator species had poor solubility in nonpolar solvents. Finally, the polymerization of methyl methacrylate with CuBr/Me-6-TREN required the use of a high concentration of catalyst and the addition of Cu(II)Cl-2 at the beginning of the reaction; the resulting polymers were of higher molecular weight than predicted by theory and had relatively broad molecular weight distributions.