In this work, we have synthesized a new type of hybridized composites, Ni-P/CNT-CNFs, which refers to carbon nanotube (CNT)-hybridized carbon nanofibers (CNFs) through electrolessly plated nickel-phosphorus (Ni-P) alloys. The composites combine the merits of CNTs with high electronic conductivity and CNFs with abundant defect sites via the junction of electrolessly deposited Ni-P. The materials have been extensively characterized by scanning electron microscope, transmission electron microscopy, X-ray diffraction, Brunauer-Emmett-Teller (BET), thermogravimetric analysis and hydrophilicity analysis. Electrochemical evaluations for oxygen reduction reaction (ORR) are carried out in 0.1 M KOH with and without 1 M methanol. In addition to serving as desirable candidates as electrocatalyst supports, the randomly oriented hybridized composites show satisfactory activities to ORR and excellent methanol tolerance in alkaline solutions. This generalized method is applicable for the preparation of a broad range of composite materials with different active components simply by variations in electroless plating bath (for example, copper\cobalt or bimetallic plating).