Air-stable trimethylplatinum(IV) β-diketonate complexes of general formula (CH3)3Pt(L)Py (L = R1COCHCOR2; R1 = R2 = CF3 (hfac), tBu (thd), CH3 (acac); R1 = CF3, R2 = tBu (ptac), CH3 (tfac); Py = pyridine) have been synthesized in high yields. The thermal properties of (CH3)3Pt(L)Py were investigated using thermogravimetry/differential thermal analysis and flow method to demonstrate their suitability as metal–organic chemical vapour deposition precursors. Thermolysis of vaporized (CH3)3Pt(acac)Py in vacuum and in the presence of hydrogen or oxygen was studied under conditions of low-pressure chemical vapour deposition using an original technique. Using this precursor, Pt films were deposited on electrodes for pacemakers under various conditions. The composition, structure, morphology and electrochemical properties of the deposited films were investigated using X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and cyclic voltammetry and LCR measurements. Pt films deposited in the presence of oxygen have a fractal-like morphology as a result the highest values of real surface areas (851–943 mm2) and capacity (5–8.5 μF mm−2).