The effects on the plasma and other conditions required to achieve population inversions between the quantum statesn=3 andn=2 of hydrogenlike ions caused by nonstatistical equilibrium fine‐structure sublevel densities are examined. Collisional and radiative transitions into and out of each of the fine‐structure sublevels (up to principle quantum numbern=5) are taken into account in a comprehensive collisional‐radiative code. Population inversions produced by both recombination and by photopumping from the 1sto 3pquantum states are examined. For electron densitiesNe≲1012Z7cm−3(whereZis the atomic number of the hydrogenlike ion), it is shown that inversions can be much more difficult to produce than is predicted by simple calculations assuming all sublevels are populated statistically.