In this study, the effect of addition of Nb on glass formation in Ni–Ti–Zr–Si–Sn alloys has been studied. The composition range for bulk glass formation with Dmax > 2 mm (Dmax, maximum diameter for glass formation by injection cast method) becomes wider when compared with the non-Nb–containing alloy. The ΔTx (= Tx – Tg; Tx, crystallization onset temperature; Tg, glass transition temperature), Trg (= Tg/Tl; Tl, liquidus temperature) and γ [= Tx/(Tl + Tg)] values for the alloys Dmax > 2 mm are in the range of 40–59, 0.638–0.651, and 0.410–0.419, respectively. The compositions of the alloys (Dmax > 2 mm) are closer to pseudo-eutectic composition than that of the alloy without Nb, showing an improved glass forming ability. The critical cooling rate for glass formation (Dmax = 5 mm) is estimated to be order of approximately 40 K/s.