Energy efficient buildings require materials with a low thermal conductivity and a high fire resistance. Traditional organic insulation materials are limited by their poor fire resistance and inorganic insulation materials are either brittle or display a high thermal conductivity. Herein we report a mechanically resilient organic/inorganic composite aerogel with a thermal conductivity significantly lower than expanded polystyrene and excellent fire resistance. Co‐polymerization and nanoscale phase separation of the phenol‐formaldehyde‐resin (PFR) and silica generate a binary network with domain sizes below 20 nm. The PFR/SiO2 aerogel can resist a high‐temperature flame without disintegration and prevents the temperature on the non‐exposed side from increasing above the temperature critical for the collapse of reinforced concrete structures. Fire not starter: Taking advantage of a co‐polymerization strategy an organic–inorganic binary network hybrid aerogel with a nanoscale homogeneity can be prepared. The phenol‐formaldehyde‐resin/SiO2 aerogel is mechanically resilient and has a thermal conductivity significantly lower than expanded polystyrene and excellent fire resistance.