In this work,series of sol-gel derived from organic-inorganic nano-hybrid composition have been prepared with inorganic tetraethyl orthosilicate (TEOS) and organic poly(ethylene glycol)(PEG). Firstly,TEOS was pre-hydrolyzed in acidic condition,then it was co-hydrolyzed and co-condensed with PEG to form organic/inorganic hybrid networks. Lanthanide ions were incorporated through the sol-gel process. Transparent organic/inorganic nano-hybrids with excellent stability and luminescent characters were obtained by the control of the processing conditions.