The synthesis of poly-acrylates, methacrylates and styrene derivatives by SET-LRP is reported in a user and environmentally friendly "green" solvent, dimethyl lactamide (DML). The occurrence of a SET-LRP mechanism in DML was demonstrated via UV-Vis spectroscopy measurements following the disproportionation of Cu(i) in the presence of N-containing ligands. The synthesis of hydrophobic and hydrophilic poly acrylate and methacrylate (methyl, n-butyl, lauryl, poly(ethylene glycol), 2-hydroxyethyl and 2-(dimethyamino)ethyl derivatives) and styrene was investigated. The controlled behaviour of the polymerisation was observed via kinetic experiments. Finally the possibility to produced well-defined polymers with functional chain-ends was demonstrated with the SET-LRP of poly(ethylene glycol) methyl ether acrylate.