An initiator containing an alkyl bromide unit and a protected amine functional group is used with CuBr/N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA), in a 1:2 molar ratio with respect to initiator concentration, in order to obtain amino-group terminated as well as halogen-free poly(methyl methacrylate) (PMMA) in a one-pot atomtransfer radical polymerization (ATRP). The terminal bromines are replaced by hydrogen atoms of the PMDETA ligand, which acts as a transfer agent. However, terminating side reactions like disproportionation or dehydrobromination occur from the beginning of the polymerization. Kinetic studies by in-line Raman spectroscopy and off-line H-1 NMR spectroscopy revealed that the controlled character of the ATRP is lost under these conditions. The measured molecular weights were consistently higher than the theoretical ones and the molecular weight distributions are relatively broad. Thermal analysis of the obtained poly(methyl methacrylate) shows two main degradation steps, one starting from unsaturated end groups (depolymerization), and one caused by main-chain scission, a further proof for the occurrence of terminating side reactions.