Present work reports the synthesis of polyethylene glycol, PEG 300 (soft segment) and toluene 2,4-diisocyanate, TDI (hard segment) based hydroxy-terminated polyurethane ligands (HTPU300) for the first time to the best of our knowledge. The effect of 3d transition metal ions with different 3d electrons within HTPU (M(II)-HTPU300, M= Mn, Co, Ni, and Zn) was evaluated by their physical and antibacterial studies of the final complex polymeric unit. M(II) HTPU300 and was conveniently synthesized in appreciable yields following a facile and one-pot addition polymerization reaction scheme. Foremost the thermal stability of all the M(II)-HTPU300 polymeric materials were evaluated using TGA, DSC, and IPDT calculations. FTIR technique was used to ascertain the structure of M(II)-HTPU300, while SEM/EDX and XRD techniques were used to study their morphology, elemental analysis, and crystalline nature of the material, respectively. Further, the in-vitro antimicrobial activity of the PU was investigated against gram-positive (Staphylococcus aureus, Bacillus subtilis) and gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacterial strains. The comparatively moderate efficacy against bacterial stain supports the possible application of such PU as thermally stable bacterial resistant materials constructed out of degradable PEG.