Perovskite quantum dots (PeQDs) endowed with capping ligands exhibit impressive optoelectronic properties and enable for cost-efficient solution processing and exciting application opportunities. We synthesize and characterize three different PeQDs with the same cubic CsPbBr₃ core, but which are distinguished by the ligand composition and density. PeQD-1 features a binary didodecyldimethylammonium bromide (DDAB) and octanoic acid capping ligand system, with a high surface density of 1.53 nm⁻², whereas PeQD-2 and PeQD-3 are coated by solely DDAB at a gradually lower surface density. We show that PeQD-1 endowed with highest ligand density features the highest dispersibility in toluene of 150 g/L, the highest photoluminescence quantum yield of 95% in dilute solution and 59% in a neat film, and the largest core-to-core spacing in neat thin films. We further establish that ions are released from the core of PeQD-1 when it is exposed to an electric field, although it comprises a dense coating of one capping ligand per four surface core atoms. We finally exploit these combined findings to the development of a light-emitting electrochemical cell (LEC), where the active layer is composed solely of solution-processed pure PeQDs, without additional electrolytes. In this device, the ion release is utilized as an advantage for the electrochemical doping process and efficient emissive operation of the LEC.