Influence of fabrication technology on field electron emission properties of nanoporous carbon (NPC) was investigated. Samples of NPC derived from different carbides via chlorination at different temperatures demonstrated similar low‐field emission ability with threshold electric field 2‐3 V/μm. This property correlated with presence of nanopores with characteristic size 0.5–1.2 nm, determining high values of specific surface area (>800 m2/g) of the material. In most cases, current characteristics of emission were approximately linear in Fowler‐Nordheim coordinates (excluding a low‐current part near the emission threshold), but the plots’ slope angles were in notable disagreement with the known material morphology and electronic properties, unexplainable within the frames of the classical emission theory. We suggest that the actual emission mechanism for NPC involves generation of hot electrons at internal boundaries and that emission centers may be associated with relatively large (20–100 nm) onion‐like particles observed in many microscopic images. Such particles can serve two functions: to provide additional “internal” enhancement of the electric field and to inhibit relaxation of hot charge carriers due to the “phonon bottleneck” effect.