Acyclic diaminocarbenes (ADCs) are powerful ligands with a broad application scope in organometallic chemistry, catalysis, photophysics and crystal engineering. Although the preparation and application of metal-ADC species are discussed in many reports, the reactivity of ADC ligands is much less scrutinised. However, studies emerged indicate that ADC ligands, in particular, those prepared via the metal-mediated nucleophilic addition to isocyanides, can be further converted into various post-functionalised derivatives. In this review, we attempt for the first time to rationalise the most important reactivity modes of metal-ADC species reported up to date.