The paper presents the results of studying the crystallization and melting processes of Ga–In eutectic alloys, which are embedded in opal matrices, using acoustic and NMR methods. The indium concentrations in the alloys were 4, 6, 9, and 15 at %. Measurements were performed upon cooling from room temperature to complete crystallization of the alloys and subsequent heating. It is revealed how the size effects and alloy composition influence the formation of phases with α- and β-Ga structures and on changes in the melting-temperature ranges. A difference was observed between the results obtained using acoustic and NMR methods, which was attributed to different temperature measurement conditions.