It has been 14 years since the discovery of the high-entropy alloys (HEAs), an idea of alloying which has reinvigorated materials scientists to explore unconventional alloy compositions and multicomponent alloy systems. Many authors have referred to these alloys as multi-principal element alloys (MPEAs) or complex concentrated alloys (CCAs) in order to place less restrictions on what constitutes an HEA. Regardless of classification, the research is rooted in the exploration of structure-properties and processing relations in these multicomponent alloys with the aim to surpass the physical properties of conventional materials. More recent studies show that some of these alloys undergo liquid phase separation, a phenomenon largely dictated by low entropy of mixing and positive mixing enthalpy. Studies posit that positive mixing enthalpy of the binary and ternary components contribute substantially to the formation of liquid miscibility gaps. The objective of this review is to bring forth and summarize the findings of the experiments which detail liquid phase separation (LPS) in HEAs, MPEAs, and CCAs and to draw parallels between HEAs and the conventional alloy systems which undergo liquid-liquid separation. Positive mixing enthalpy if not compensated by the entropy of mixing will lead to liquid phase separation. It appears that Co, Ni, and Ti promote miscibility in HEAs/CCAs/MPEAs while Cr, V, and Nb will raise the miscibility gap temperature and increase LPS. Moreover, addition of appropriate amounts of Ni to CoCrCu eliminates immiscibility, such as in cases of dendritically solidifying CoCrCuNi, CoCrCuFeNi, and CoCrCuMnNi.
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