A library of novel structurally related singlet carbenes, namely, acyclic amino(haloaryl)carbenes, was designed by a high-yielding two-step procedure, and their chemical stability explored both experimentally and theoretically. Thanks to a careful selection of both the amino and the aryl substitution pattern, these carbenes exhibit a wide range of stability and reactivity, spanning from rapid self-dimerization for carbenes featuring ortho-F substituents to very high chemical stability as bare carbenes, up to 60 °C for several hours for compounds carrying ortho-Br substituents. Their structure was determined through NMR and X-ray diffraction studies, and their reactivity evaluated in benchmark reactions, highlighting the ambiphilic character of this novel class of singlet carbenes. In contrast with previously reported aryl substituents incorporating o-CF3 and t-Bu groups, which were considered “spectator”, the high chemical stability of some of these carbenes relates to the stabilization of the σ-orbital of the carbene center by the π-accepting haloaryl substituent through delocalization. Kinetic protection of the carbene center is also provided by the ortho-halogen atoms, as demonstrated computationally. This push-pull stabilization effect makes acyclic amino(haloaryl) carbenes among the most ambiphilic stable carbenes reported to date, holding promise for a variety of applications.