N-doped hollow porous carbon materials have attracted significant scientific interest in the field of peptide adsorption, drug delivery and catalysis. However, their facile synthesis is still a challenge due to the lack of an ideal template and effective route for high specific surface area (SSA). In this work, we report a facile approach for preparing N-doped hollow porous carbon whiskers (HPCWs) by using CaCO3 whiskers as a green template and double inner-activating agent. Two inner activators, CO2 and Ca(OH)2, are generated from the CaCO3 whisker template during the carbonization process. Among them, Ca(OH)2 was formed by H2O vapors reacting with the remaining template CaO. Attributed to the drastic synergistic effect of inner-activation (CO2 or Ca(OH)2) and outer-activation (KOH), the synthesized HPCWs exhibit ultrahigh SSA (3007 m2 g-1), the largest pore volume (2.63 cm3 g-1) and a controllable proportion of micropores (Sm/St, 60-86%). These intriguing pore structure characteristics of HPCWs endow with them rich target-oriented applications, as exemplified by their outstanding adsorption for casein hydrolysate (10 080 mg g-1), which is two orders of magnitude (102) higher than that of common porous materials. This facile and green synthesis strategy may pave a new way to prepare hollow porous carbon materials with the desired pore structure and high surface area for numerous applications.