Abstract The advancement of electrochemical energy storage is closely bound up with the breakthrough of controllable fabrication of energy materials. Inspired by a popcorn fabrication from corn raw, herein a unique porous macrocellular carbon composed of cross‐linked nano/microsheets by a powerful puffing of rice precursor is described. The rice is directly puffed with a volume enlargement of ≈20 times when it is instantaneously released from a sealed environment with a high pressure of 1.0 MPa at 200 °C. Interestingly, when metal (e.g., Ni) nanoparticles are embedded in the puffed rice derived carbon (PRC), high‐quality PRC/metal composites are achieved with attractive properties of a high electrical conductivity of ≈7.2 × 10 4 S m −1 , a large porosity of 85.1%, and a surface area of 1492.2 m 2 g −1 . The PRC/Ni are employed as a host in lithium–sulfur batteries. The designed PRC/Ni/S electrode exhibits a high reversible capacity of 1257.2 mA h g −1 at 0.2 C, a prolonged cycle life (821 mA h g −1 after 500 cycles), and enhanced rate capability, much better than other counterparts (PRC/S and rGO/S). The excellent properties are attributed to the advantages of PRC/Ni network with a high electrical conductivity, strong adsorption/blocking ability for polysulfides, and interconnected porous framework.