Pt nanoparticles (PtNPs) well-dispersed on thiolated polyaniline (TPANI)-multiwalled carbon nanotubes (MWCNTs) were prepared for enhanced electrocatalytic oxidation of methanol in acidic media. Briefly, the preparation of nanocomposites was carried out via microwave-assisted thiol–ene reaction of 2,5-dimercapto-1,3,4-thiadiazole (DMcT) with oxidized PANI, which was synthesized in the presence of MWCNTs, yielding TPANI-MWCNTs; then, PtNPs were deposited on TPANI-MWCNTs by a microwave-assisted method to obtain PtNPs/TPANI-MWCNT nanohybrids. Fourier transform infrared spectroscopy, cyclic voltammetry (CV), transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and inductively coupled plasma-atom emission spectroscopy were used to study relevant nanohybrid properties. TEM showed that PtNPs were well dispersed on TPANI-MWCNTs. TGA showed that PtNPs/TPANI-MWCNTs exhibited better thermal stability than PtNPs/TPANI-MWCNTs and PtNPs/MWCNTs. CV studies showed that PtNPs/TPANI-MWCNT-modified glassy carbon electrode (GCE) exhibited a larger electrochemically active surface area and higher electrocatalytic performance toward methanol electro-oxidation compared with those of PtNPs/PANI-MWCNTs/GCE and PtNPs/MWCNTs/GCE. Also, the PtNPs/TPANI-MWCNTs/GCE electrode possessed high stability and maintained 86% of its initial catalytic activity after 1000-cycle CV in 1.0 M CH₃OH + 0.5 M H₂SO₄.