Non-toxic, highly-active and robust complexes are the holy grail as ideal green catalysts for the polymerisation of biobased and biodegrable polylactide. Four new zinc guanidine complexes [ZnCl2(TMG4NMe2asme)], [ZnCl2(TMG5Clasme)], [ZnCl2(TMG5Measme)] and [ZnCl2(TMG5NMe2asme)] with different electron-donating and electron-withdrawing groups on aromatic backbone of the ligand have been synthesised. Ligands are derived from low-cost commercially available compounds and have been converted in a three- or four-step synthesis into the desired ligand in good yields. The compounds have been fully characterised and tested in the ROP of rac-LA in the melt under industrially relevant conditions. The complexes are based on the recently published structure [ZnCl2(TMGasme)] which has shown high activity in the polymerisation of lactide at 150 °C. Different substituents in the para-position to the guanidine moiety significantly increase the polymerisation rate whereas positioning substituents in meta-position causes no change in the reaction rate. With molecular weights over 71 000 g mol-1, the best catalyst produces polymer for several industrial applications and its polymerisation rate approaches the one of Sn(Oct)2. The robust systems are able to polymerise non-purified lactide. The initiation of the polymerisation is suggested to occur by impurities in the monomer.