A novel composite was constructed by the in situ growth of silver nanowires (AgNW) on multi-walled carbon nanotubes (MWCNT). Firstly, thiol groups were covalently bonded onto the surface of MWCNT by the esterification of thioglycolic acid with hydroxylated MWCNT. Reduced platinum (Pt) nanoparticles were then attached to the MWCNT via the thiol groups. In the presence of poly(vinyl pyrrolidone), Pt nanoparticles served as seeds for generating AgNW of uniform diameter. Finally, a MWCNT/AgNW composite with a conductive network structure was fabricated. The structure and morphology of the composite were measured by a variety of methods, including UV-visible extinction spectrometry, energy-dispersive spectrometry, X-ray diffractometry, Raman spectrometry and electron microscopy. An electrically conductive thin film of 80% transparency with a sheet resistance of 47.8 Ω sq⁻¹ was prepared by coating the composite onto a polyethylene terephthalate film substrate.