SnO2 aerogels were successfully synthesized by using SnCl4, ammonium hydroxide (AH), formamide, propylene oxide, and tetraethoxysilane as tin source, reaction promoter, drying control chemical additive (DCCA), gel accelerator, and surface modifier, respectively, via the sol–gel method, combined with subsequent ambient pressure drying of sol–gel. The results of Fourier transform infrared spectroscopy proved that the CH3CH2OSi-bond was transferred to SnO2 gel. A contact angle measuring instrument was utilized for the study of hydrophicity and hydrophobicity of SnO2 aerogels, and the complete porous skeleton structure of SnO2 aerogels was confirmed by field emission scanning electron microscopy (FESEM) and nitrogen adsorption–desorption analyzer, denoting AH allowed SnO2 aerogels to shape more macropores. Based on the thermal resistance tester, it showed that the SnO2 aerogels had low thermal conductivity. The biggest specific surface area and lowest thermal conductivity of SnO2 aerogels were 447.26 m2/g and 0.0717 K/(m•K), respectively.