Silicone porous materials are relatively inert and do not react easily with some chemicals or oils. Concomitantly, due to their hydrophobic nature, silicone sponges can be used to absorb oil from the mixture with water. Their properties make silicone foams of interest for a wide range of applications, such as gas storage and gas separation, catalysis, detection, in the aerospace industry and transport industry. Amino-functionalized polysiloxanes represent an adjustable platform for the ex-pansion of porous silicones. In the presence of ammonium bicarbonate as a porogenic agent, a series of porous silicone networks were prepared and processed in the form of films. The cross-linking of the pendant functionalized polysiloxanes was realized using TEOS through the Si-OH chain end groups. The silicone networks differ by the content of amino groups in the polymer precursor and by the amount of porogenic agent used in their preparation process. The CO2 react with NH2 groups forming dynamic, thermoreversible carbamate bridges, as shown in the IR study. The new silicone networks have good thermal and mechanical properties and high dielectric permittivity. Being porous materials, they can be applied in environmental applications for CO2 capture. Copolymers of dimethylmethyl(3-aminopropyl)siloxane with silanol groups as chain ends and different contents (6.4, 9.8 and 100 mol%) of pendant aminopropyl groups were used to obtain porous silicone networks. The morphology was generated by the decomposition of added ammonium bicarbonate, which acts as a degradative chemical blowing agent (CBA), by heating in the presence of acetic acid. The latter also promotes cross-linking by condensation with TEOS at the same time, replacing the organometallic compound (e.g. DBTDL) often used as a catalyst for this purpose. In the presence of CO2 from CBA decomposition, as in air, amine groups are partially carbonated or converted to carbamates that form reversible interchain bridges, capable of being broken down by heating and reformed by cooling in the normal atmosphere. These facts make these materials suitable for environmental applications.