The low melting element gallium was utilized as a metal melt together with the azole 1, 2,4,‐1H‐triazole for the synthesis of the homoleptic framework 3∞[Ga(Tz)3], Tz– = 1, 2,4‐triazolate. The framework is formed at 180 °C at the phase border of two liquid phases, gallium and the azole, which do not mix with one another. Thus, 1, 2,4,‐1H‐triazole is also in molten state. The homoleptic triazolate adopts the CoAs3 structure and a (4, 6) net topology, exhibiting good thermal stability of 440 °C.