A set of pentacoordinated dimethyltin(IV) complexes of flexible N‐protected amino acids and fluorinated β‐diketone/β‐diketones was screened for their antibacterial activity against Pseudomonas aeruginosa, Staphylococcus aureus and Streptomyces griseus. These pentacoordinated complexes of the type Me2SnAB (where : R = CH(CH3)C2H5, A1H; CH2CH(CH3)2, A2H; CH(CH3)2, A3H; CH2C6H5, A4H; and BH = R'C(O)CH2C(O)R″: R′ = C6H5, R″ = CF3, B1H; R′ = R″ = CH3, B2H; R′ = C6H5, R″ = CH3, B3H; R′ = R″ = C6H5, B4H) were generated by the reactions of dimethyltin(IV) dichloride with sodium salts of flexible N‐protected amino acids (ANa) and fluorinated β‐diketone/β‐diketones (BNa) in 1:1:1 molar ratio in refluxing dry benzene solution. Plausible structures of these complexes were elucidated on the basis of physicochemical and spectral studies. 119Sn NMR spectral data revealed the presence of pentacoordinated tin centres in these dimethyltin(IV) complexes.