Fabrication of Sm2+-doped silicate glasses possessing interconnected macropores has been attempted via two different procedures utilizing a phase-separation phenomenon; one includes liquid-liquid phase separation of macroscopically uniforrn melt-quenched glasses under heat treatment, and the other polymerization-induced phase separation in alkoxy-derived sol-gel systems. Macroporous silicate glasses doped with Sm2+ can be successfully prepared via the sol-gel method.