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The dielectric characteristics of nano-Al2O3 composite polyimide film with Al2O3 content of 5%, 10%, 12.5%, 15% and 20% in weight ratio were measured, respectively. The permittivity, dissipation factor and TSC peak temperature increase with increasing of the inorganic content. A percolation threshold corresponding to the content between 12.5% and 15% was discovered. With increasing the Al2O3 content, breakdown strength decrease and conductivity increases. The active energy of composite films with different inorganic content, ranging from 0.58 to 0.89, was calculated by auto-separating technology.