MXenes are two-dimensional transition-metal carbides and nitrides with an attractive combination of physicochemical properties, gaining notable potential in many applications. Currently, MXene synthesis is mainly performed from powder precursors whose purity and grain size define the quality and flake size of 2D sheets, typically not exceeding 2–3 μm. In this work, we successfully synthesize macroscopic nanolayered V2CTz MXenes with lateral dimensions larger than 25 μm from a V2AlC single crystal by exploiting a new strategy based on ion implantation. Ne2+ ion implantation of the single-crystal precursor is applied to introduce defects in the crystal structure of V2AlC, which facilitates chemical etching and drastically reduces the etching time down to 8 h (∼10 times lower as compared to conventional synthesis from powder precursors). The quality and morphology of exfoliated macroscopic MXene multilayers have been comprehensively studied by performing detailed analyses based on different kinds of microscopies and spectroscopies. The obtained macroscopic flakes are ideal objects to study the intrinsic physical properties of V2CTz MXenes and explore their potential application, in particular, as membranes.