The desire for lightweight nanoporous materials with high-performance thermal insulation and efficient anti-ablation resistance for energy conservation and thermal protection/insulation has greatly motivated research and development recently. The main challenge to synthesize such lightweight materials is how to balance the relationship of low thermal conductivity and flame retardancy. Herein, we propose a new concept of lightweight "rime-like" structured carbon-phenolic nanocomposites to solve this problem, where the 3D chopped network-structured carbon fiber (NCF) monoliths are incorporated with nanoporous phenolic aerogel to retain structural and functional integrity. The nanometer-scaled porous phenolic (NP) was synthesized through polymerization-induced phase separation and ambient pressure drying using phenolic resin (PR) solution as reaction source, ethylene glycol (EG) as solvent and hexamethylenetetramine (HMTA) as catalyst. We demonstrate that the as-prepared NCF-NP nanocomposite exhibits with a low density of 0.25-0.35 g/cm(3), low thermal conductivity of 0.125 Wm(-1)K(-1) and outstanding flame retardancy exceeding 2000 °C under arc-jet wind tunnel simulation environment. Our results show that the synthesis strategy is a promising approach for producing nanocomposites with excellent high-temperature heat blocking property.