Bi-functional effect, elevated mass transport and increased durability have been combined within one catalyst for electrochemical methanol oxidation reaction. It has niobium (Nb) doped titanium dioxides (TiO2) nanosized half-sphere shell (HSS) as the substrate material deposited with small amount of Pt nanoparticles. These specially designed HSS nanostructure has significantly increased surface areas which are suitable for Pt nanoparticles to be deposited onto them to form the catalyst denoted as Pt/Nb-TiO2 HSS. It exhibits a remarkably high methanol oxidation activity of 0.21 V vs. RHE which is 0.05 V lower than HiSPEC10000 PtRu/C catalyst, due to the substrate's strong metal support interactions effect, bi-functional effect and the special structure. These HSS nanostructures have also increased the methanol diffusion and mass transport within the anode to give a maximum power output of 0.0931 W of cathode polarization in miniature direct methanol fuel cell (DMFC). It also acts as protection shells, which minimises the dissolution of Pt metal nanoparticles to prevent its diffusion through the membrane.