Mn2+-doped Zn2SiO4 inverse opals were synthesized by sol-gel technique combined with the self-assembly of the opal template. Zn2SiO4:Mn2+ precursors were infiltrated into the interstices of the opal template assembled by polystyrene spheres. The polystyrene template was removed by calcining and nanocrystals of Mn2+-doped Zn2SiO4 were obtained in the void of opal template. The inverse opals show photonic crystal behavior and emit yellow light initially with the luminescent peak at 562 nm corresponding with the fact that β-phase is the dominant phase for nanocrystals less than 30nm. As the β-phase transformed to α-phase with the gradual increase of treating temperature and the growth of the crystal, the luminescence from Zn2SiO4:Mn2+ phosphors change from yellow to green.