Eu-doped silicate complex gel nano-particles was obtained by sol-gel process and characterized with TEM, XRD, PL, etc. The well dispersed particles have particle size about 60～70 nm with specific surface area 98.3 m2·g-1. The complex gel phosphor gives a broad and strong luminescent emission originating from Eu2+ ions centered at 425 nm. The emission band shifts to shorter wavelengths with the increase of the ion radius of the alkali earth metals, but the band becomes red-shifted gradually with the increase of the ion radius of the alkali metals(except Li+). These divalent Eu2+ ions originate in inequivalent substitution of the alkaline earth ions. The presence of alkaline ions is favorable for the increasing emission intensity of the Eu2+ and lowering crystalline temperature of the silicate complex gel.