We synthesized Bulk Metallic Glass (BMG) matrices using the general formula [Ni-(Mo/Cr)-Si]100−x:[Ti/Nb]x (x = 0–15 at.%) via mechanical high energy ball milling technique. Among them, one best sample is targeted in each series, based on their superior structural, thermal, mechanical and corrosion properties which are labeled as - NMST6 ((Ni75Mo15Si10)94Ti6), NMSNb10 ((Ni75Mo15Si10)90Nb10), NCST8 ((Ni75Cr15Si10)92Ti8) and NCSNb6 ([Ni-Cr-Si]94[Nb]6). The results revealed that mixing of optimum quantities of Ti/Nb content in the present BMG network helped to avoid embrittlement, overcome strain cracking problems, prevent pitting, and improved corrosive resistance which is essential to suit aerospace and lightweight vehicle applications. The variation in thermal (ΔT, Trg), mechanical (σy, εp, hardness) and potentiometric parameters (Ec, ic, Ep, ip) of all the targeted samples explained in the light of structural variation and glass modifying features due to the substitution of Ti/Nb in optimum quantities.