Integrating nitrogen species into sp²-hybridized carbon materials has proved an efficient means to improve their electrochemical performance. Nevertheless, an inevitable mixture of nitrogen species in carbon materials, due to the uncontrolled conversion among different nitrogen configurations involved in synthesizing nitrogen-doped carbon materials, largely retards the precise identification of electrochemically active nitrogen configurations for specific reactions. Here, we report the preparation of single pyrrolic N-doped carbon materials (SPNCMs) with a tunable nitrogen content from 0 to 4.22 at.% based on a strategy of low-temperature dehalogenation-induced and subsequent alkaline-activated pyrolysis of 3-halogenated phenol-3-aminophenol-formaldehyde (X-APF) co-condensed resins. Additionally, considering that the pseudocapacitance of SPNCMs is positively dependent on the pyrrolic nitrogen content, it could be inferred that pyrrolic nitrogen species are highly active pseudocapacitive sites for nitrogen-doped carbon materials. This work gives an ideal model for understanding the contribution of pyrrolic nitrogen species in N-doped carbon materials.