Novel phenomena and methods related to dielectronic capture and dielectronic recombination are studied for non-local thermodynamic equilibrium (LTE) plasmas and for applications to non-LTE ionization balance. It is demonstrated that multichannel autoionization and radiative decay strongly suppress higher-order contributions to the total dielectronic recombination rates, which are overestimated by standard approaches by orders of magnitude. Excited-state coupling of dielectronic capture is shown to be much more important than ground-state contributions, and electron collisional excitation is also identified as a mechanism driving effective dielectronic recombination. A theoretical description of the effect of angular-momentum-changing collisions on dielectronic recombination is developed from an atomic kinetic point of view and is visualized with a simple analytical model. The perturbation of the autoionizing states due to electric fields is discussed with respect to ionization potential depression and perturbation of symmetry properties of autoionization matrix elements. The first steps in the development of statistical methods are presented and are realized in the framework of a local plasma frequency approach. Finally, the impact of collisional–radiative processes and atomic population kinetics on dielectronic recombination is critically discussed, and simple analytical formulas are presented.