Hybrid polyionic complexes (HPICs), constructed from double-hydrophilic block copolymers and metal ions, have been largely developed with increasing interest in the past decade in the fields of catalysis, materials science and biological applications. The chemical natures of both blocks are very versatile, but one block should be able to interact with ions, and the second one should be neutral. Many metals have been used to form HPICs, which have, in their simplest architectural form, a core-shell structure of a few tens of nanometers in radius with an external shell made of the neutral block of the copolymer. In this review, we focus our discussion on the stability, shape, size and inner structure of these hybrid micelles. We then describe the most recent applications of HPICs, as reported in the literature, and point out the current challenges, missing structural information and future perspectives for this class of organized structures.