Composite polymer electrolytes based on polyethylene oxide(PEO) were prepared by using LiClO4 as doping salt and silane-modified SiO2 as filler. SiO2 was formed in-situ in (PEO)8LiClO4 matrix by the hydrolysis and condensation reaction of Si(OC4H9)4. The crystallinity, morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry, scanning electron microscopy, atom force microscopy and alternating current impedance spectroscopy, respectively. Compared with the crystallinity of the unmodified SiO2 as inert filler, that of composite polymer electrolytes is decreased. The results show that silane-modified SiO2 particles are uniformly dispersed in (PEO)8LiClO4 composite polymer electrolyte film and the addition of silane-modified SiO2 increases the ionic conductivity of the (PEO)8LiClO4 more noticeably. When the mass fraction of SiO2 is about 10%, the conductivity of (PEO)8LiClO4-modified SiO2 attains a maximum value of 4.8×10−5 S·cm−1.