VIA melt-quenching route, crystallization in the ternary Bi2O3-CaO-CuO glass was studied. The preparation of six samples within the ternary triangle gave two glasses and four devitrified glasses. The thermal effect pointed to softening and crystallization temperatures between 290°C and 422 °C and between 360°C and 550 °C, respectively. The crystallized phases within the former heat-treatment were mixed oxides of bismuth, copper and calcium; however its ratios in oxide formula were different according to the composition. The microstructure of the devitrified samples show heterogenous crystallization in residual glass containing nano-scale crystals however, in the glassy samples scattered clusters containing more nano-scale crystals in glassy groundmass.