Nanoporous silicone resins and silicone resin films having low dielectric constants and a method for preparing such nanoporous silicone resins. The silicone resin comprises the reaction product of a mixture comprising (A) 15-70 mol % of a tetraalkoxysilane described by formula Si(OR1)4,  where each R1 is an independently selected alkyl group comprising 1 to about 6 carbon atoms, (B) 12 to 60 mol % of an organosilane described by formula R4SiX3,  where R4 is selected from the group consisting of alkyl groups comprising 1 to about 6 carbon atoms and phenyl and each X is an independently selected hydrolyzable substituent, (C) 15 to 70 mol % of an organotrialkoxysilane described by formula R2Si(OR3)3,  where R2 is a hydrocarbon group comprising about 8 to 24 carbon atoms or a substituted hydrocarbon group comprising a hydrocarbon chain having about 8 to 24 carbon atoms and each R3 is an independently selected alkyl group comprising 1 to about 6 carbon atoms; in the presence of (D) water, (E) hydrolysis catalyst, and (F) organic solvent for the reaction product. The silicone resin is cured and heated in preferably an inert atmosphere at a temperature sufficient to effect thermolysis of carbon-carbon bonds of the R2 groups thereby forming a nanoporous silicone resin.