Nitrogen-enriched porous carbon materials have been successfully synthesized via a template carbonization method, in which nicotinic acid acts as carbon/nitrogen sources, and Ca(OAc)2 · H2O as a template. It reveals that the mass ratio of Ca(OAc)2 · H2O-to-nicotinic acid and the carbonization temperature dominate the morphology of carbon materials as well as capacitive performances. The sample obtained with the ratio of Ca(OAc)2 · H2O-to-nicotinic acid as 1.5 at 800℃, namely the C-1.5-800 sample, displays the optimum capacitive behavior. It is amorphous with low-graphitization degree, possessing hierarchical porous structure, high nitrogen content (14.5%), large specific surface area (788 m2 g-1) and high total pore volume (3.56 cm3 g-1). As a result, the as-made C-1.5-800 electrode exhibits a maximum specific capacitance of 216 F g-1 at a current density of 1 A g-1 in 6 M KOH aqueous solution. It also displays a maximum energy density of 45.9 Wh kg-1 at 2050 W kg-1 and a maximum power density of 20100 W kg-1 at 19.2 Wh kg-1 at operation temperature of 50℃ in [EMIm]BF4/AN organic electrolyte. More importantly, the C-1.5-800 electrode exhibits an excellent cycling stability within 5000 cycles at 5 A g-1. This work may enrich and broaden the field of porous carbon and its potential application for supercapacitors under high temperature.