Mesoporous nickel phosphate/carbon fibers nanocomposite (Nano-CF/NiPh) shows Type IV isotherm with H4 hysteresis loop as evident form N-2 adsorption/desorption measurements. NiPh is fabricated by cost-effective reflux method and the crystalline mesoporous structure is proved by different surface and structure instrumentations including [Brunauer-Emmett-Teller] surface area measurements, transmission electron micrograph with selected-area electron diffraction, FE-SEM and XRD. Impregnation of CF (20% by weight) onto the NiPh powder has found great impacts on the surface, electrochemical and catalytic characteristics of the Nano-CF/NiPh. This is attributed to the enhanced specific surface area of Nano-CF/NiPh (84.3 m(2)g(-1)) compared to NiPh (19.0 m(2)g(-1)) and to the increase in the electrochemically active surface area. Electrochemical oxidation of ethanol on the Nano-CF/NiPh has shown better performance than electrocatalysts cited in literatures. Important kinetic and transport parameters have been calculated and compared with literatures. The process takes advantages of the mesoporous structure of the NiPh, high electronic conductivity of the CF and the stability of the phosphate matrix.