Nanoporous three-dimensional networks of polyurethane particles, e.g., polyurethane aerogels, and methods of preparation are presented herein. Such nanoporous networks may include polyurethane particles made up of linked polyisocyanate and polyol monomers. In some cases, greater than about 95% of the linkages between the polyisocyanate monomers and the polyol monomers are urethane linkages. To prepare such networks, a mixture including polyisocyanate monomers (e.g., diisocyanates, triisocyanates), polyol monomers (diols, triols), and a solvent is provided. The polyisocyanate and polyol monomers may be aliphatic or aromatic. A polyurethane catalyst is added to the mixture causing formation of linkages between the polyisocyanate monomers and the polyol monomers. Phase separation of particles from the reaction medium can be controlled to enable formation of polyurethane networks with desirable nanomorphologies, specific surface area, and mechanical properties. Various properties of such networks of polyurethane particles (e.g., strength, stiffness, flexibility, thermal conductivity) may be tailored depending on which monomers are provided in the reaction.