Atom transfer radical polymerization (ATRP) of menthyl acrylate (MnA) was performed with different catalytic systems. ATRP of MnA proceeds in a controlled/living manner as evidenced by narrow polymer polydispersity (< 1.20), but with a very slow polymerization rate using 1-phenylethyl bromide (1-PEBr) or ethyl 2-bromopropionate (2-EBP) as initiators (monomer/initiator = 100/1) and N,N,N',N',N' '-pentamethyldiethylenetriamine (PMDETA) as ligand. Only 5.7% and 14.8% monomer conversion were obtained within 4 h using 1-PEBr and 2-EBP, respectively. In contrast, replacing the PMDETA ligand with 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (Me(4)cyclam) promotes a very fast but uncontrolled polymerization (97.1% conversion in 1 h with a polydispersity as broad as 1.70). However, a controlled/living polymerization system of MnA (with a relatively fast polymerization rate, 78.4% conversion in (1)/(2) h; M-n = 14 000 g/mol; M-w/M-n = 1.11) was achieved by using tris[2-(dimethylamino)ethyl]amine (Me6TREN) as ligand. The controlled/living feature of this system allowed the chain extension polymerization of methyl acrylate (MA) to synthesize the block copolymer, poly(menthyl acrylate)-block-poly(methyl acrylate) [PMnA-b-PMA]. The thermal stability of PMnA was investigated by thermogravimetric analysis (TGA) and gas chromotography/mass spectrometry (GC/MS). The pyrolysis of PMnA (with the release of menthenes) provides an alternative route to synthesize poly(acrylic acid) with controlled structures from PMnA (prepared by ATRP of MnA).