Preparation of aluminide coatings, AlxVy, is a key step for the formation of V-Al/Al2O3 as tritium permeation barrier (TPB) on V alloys. We firstly attempted to process aluminide coatings on V-5Cr-5Ti by a two-step process of electrochemical Al deposition (ECA) and heat treatment. Al deposition from AlCl3-1-ethyl-3-methyl-imidazolium chloride (AlCl3-EMIC) ionic liquid was performed at room temperature, with current density varying from 8 to 32 mA/cm(2). Homogeneous and well adherent Al coatings on V-5Cr-5Ti were obtained by galvanostatic electrodeposition at 20 mA/cm(2), with the deposition rates up to 21 mu m/h. And then Al-coated specimens were heated in flowing Argon gas, forming aluminide coatings. The aluminide coatings exhibited a double-layer or almost a single-layer structure, and their thickness increased with temperature, time and Al-coating thickness, respectively. Main phase of coatings was Al-3(V, Cr, Ti) at initial diffusion stage, and then gradually transformed into Al-3(V, Cr, Ti)(5), and next to V(Al, Cr, Ti) solid solution, with double-layer structure transforming into single-layer structure. The homogenous layer of Al-8(V, Cr, Ti)(5) is the appropriate aluminide for further selective oxidation. The optimum aluminized conditions and growth kinetics of Al-8(V, Cr, Ti)(5) were obtained. (c) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.