The temperature evolution of the Ga94In6 liquid alloy introduced into an opal matrix has been studied by the NMR method in the temperature range 300–155 K. The temperature dependences of the position and the intensity of the NMR signals from 71Ga, 69Ga, and 115In isotopes have been measured upon cooling and heating of the nanocomposite. The 71Ga NMR line has been observed to be split into two components on cooling below 176 K with a transfer of the intensity to the high-frequency component. The results demonstrate an induced by nanoconfinement shift of the eutectic point in the alloy and the liquid–liquid phase transition in the indium depleted part of the melt.