Alloying of Ga with Se is observed in elemental Ga:Se=50:50 mixture upon high-energy ball milling. X-ray diffraction of samples milled in the range displays evidence of hexagonal gallium selenide (GaSe). At longer milling times two wide bands are superimposed on the crystalline pattern, indicating that the main milling product at longer t is an amorphous phase. Differential scanning calorimetry shows that the amorphous phase is a Ga–Se phase and that it grows in concentration with t. Raman scattering provides modes of both amorphous and crystalline GaSe phases.