One of the major problems in Li-ion battery is fire accident and explosive due to usages of organic liquid electrolytes. Currently, we tried to use an alternative solid polymer electrolyte in Li-ion batteries in order to reduce their fire hazardous related problem. We have synthesized the solgel silica immobilized polyvinylidene fluoride (PVDF) with combination of dihydrogen ammonium phosphate (DHAP) based solid polymer electrolyte. Further, CaO (Egg shell calcined at 1000 ^oC) was used as filler to enhance their ionic conductivity. Silica NPs were uniformly dispersed onto polymer matrix (Approx. 132 nm) analysed by particle size measurement. The prepared solid polymer electrolyte has better thermal stability (400 ^oC), mechanical strength and amorphous behaviour demonstrated by TGA, Tensile tester and XRD. The effect of different percentages of silica/DHAP/CaO in the polymer matrix was investigated their cyclic stability, charge/discharge and ionic conductivities. The novel green polymer solid electrolyte effectively used as separator in solid state Li-ion batteries.