In the present work, we report the formation of a porous oxide/hydroxide surface layer on the Ti-29Nb-13Ta-4.6Zr (TNTZ) alloy achieved by the combination of an alkali immersion and a potential pulse polarisation process. The alkali treatment has been employed for pure titanium to produce amorphous and porous layer prior to hydroxyapatite (HAp) growth. But, in the case of TNTZ, immersion in 5M NaOH at the open circuit potential (OCP) at 60°C for 24 hours, did not yield any uniform layer, instead a thick deposited layer with highly cracked one. The cracks were attributed to the growth of a tantalum enriched particulate. In order to avoid the crack formation, the electrochemical behaviour of the alloy and the pure alloying elements (Ti, Nb, Ta and Zr) was investigated to produce a uniform surface with the application of a square wave modulated potential pulse polarization, leading to the formation of a relatively uniform porous layer on the alloy.