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MAX phases are layered solids with unique properties combining characteristics of ceramics and metals. MXenes are their two‐dimensional siblings that can be synthesized as van der Waals‐stacked and multi‐/single‐layer nanosheets, which possess chemical and physical properties that make them interesting for a plethora of applications. Both families of materials are highly versatile in terms of their chemical composition and theoretical studies suggest that many more members are stable and can be synthesized. This is very intriguing because new combinations of elements, and potentially new structures, can lead to further (tunable) properties. In this review, we focus on the synthesis science (including non‐conventional approaches) and structure of members less investigated, namely compounds with more exotic M‐, A‐, and X‐elements, for example nitrides and (carbo)nitrides, and the related family of MAB phases.