The melting and solidification behavior of Alloy 625 has been investigated with differential thermal analysis (DTA) and electron microscopy. A two-level full-factorial set of chemistries involving the elements Nb, C, and Si was studied. DTA results revealed that all alloying additions decreased the liquidus and solidus temperatures and also increased the melting temperature range. Terminal solidification reactions were observed in the Nb-bearing alloys. Solidification microstructures in gas-tungsten-arc welds were characterized with transmission electron microscopy (TEM) techniques. All alloys soldified to an austenitic (γ) matrix. The Nb-bearing alloys terminated solidification by forming various combinations of γ/MC(NbC), γ/Laves, and γM6C eutectic-like constituents. Carbon additions (0.035 wt pct) promoted the formation of the γ/MC(NbC) constituent at the expense of the γ/Laves constituent.