This work presents the hydrothermal synthesis of hierarchical TiO2 nanorods (NRs) grown for the first time from a pulsed laser deposited Ti seed layer on carbon paper (CP) substrate without the use of templates or binders. XRD reveals that TiO2-NRs crystallize in rutile phase. The as-prepared TiO2-NRs greatly enhances the electroactivity and stability of Pt towards ethanol oxidation reaction. Durability studies with chronoamperometry show the specific mass activity of the Pt/TiO2-NRs/CP catalyst is 47.92 mA mg−1 that is 7 times superior to that of the Pt commercial (6.72 mA mg−1). The Pt/TiO2-NRs/CP as anode in a membraneless microfluidic ethanol fuel cell delivers a maximum current density of 56.4 mA cm−2 and 5.1 mW cm−2 and a durability similar to commercial Pt anode of which the Pt loading is 16.7 higher than the Pt/TiO2-NRs/CP catalyst. This performance can be credited to the 3-D open porous interface built of hierarchical TiO2-NRs, which offers favorable electrolyte accessibility, better stability and straight pathways for the movement of electrons towards the electrode. Finally, the free-standing nature, the low platinum loading and the high stability make the TiO2-NRs/CP a promising catalyst support for fuel cell technologies.