To augment the wear resistance of the titanium alloy, electroless nickel (EN) is an effective method to strengthen the surface properties. However, the oxide layer on the surface of titanium alloy will inhibit the adhesion of EN. Meanwhile, the traditional pretreatment methods are cumbersome steps and time-consuming. To overcome these limitations, this study systematically explores a one-step pretreatment approach through amino tris(methylenephosphonic acid) (ATMPA) and HF, which is designed to improve the binding strength of EN. The results exhibit that the compact composite membrane with Ti-ATMPA and TiF3 are successfully prepared under pH 3.0, which has provided a pretreatment layer to replace the oxidation of titanium alloy during EN process, and the adhesion of EN coating (EN-3.0) based on the pretreatment layer reaches 22.46 MPa. The wear resistance of titanium alloy and EN plating system studied via a friction measurement, and the lowest wear rate exhibit in EN-3.0 plating (880.9 × 10-10mm3/Nm) that is lower than EN-traditional pretreatment with a decrease of 32 %. Moreover, the formation and catalytic model of medial layer are also discussed.