Nitrogen interstitials (normalNnormali) have the lowest formation energy among intrinsic defects of hexagonal boron nitride (hBN) under n‐type and N‐rich conditions. Using an optimized hybrid functional, which reproduces the gap and satisfies the generalized Koopman's condition, an normalNnormali configuration is found, which is lower in energy than the ones reported so far. The (0/–) charge transition level is also much deeper, so normalNnormali acts as a very efficient compensating center in n‐type samples. Its calculated photoluminescence (PL) at 3.0 eV agrees well with the position of an N‐sensitive band measured at 3.1 eV. It is also found that the nitrogen vacancy (normalVnormalN) cannot be the origin of the three‐boron‐center (TBC) electron paramagnetic resonance (EPR) center and in thermal equilibrium it is even unlikely to exist in n‐type samples.