Since the discovery of graphene, two-dimensional (2D) materials have been receiving increased attention. The quest for new 2D materials with unique structure and special properties has become urgent. Herein we report on the preparation of a new kind of ternary 2D material, Ti₄AlN₃ nanosheets, by liquid exfoliation of the corresponding laminated MAX phase. The obtained Ti₄AlN₃ nanosheets, bearing abundant surface groups, can be further used to fabricate micro-patterns via micro-contact printing (μCP) and subsequently functionalized through self-initiated photografting and photopolymerization (SIPGP) to achieve MAX-based hybrid patterned polymer brushes. Our work opens a door to explore the synthesis of 2D hybrid materials for functional applications based on the traditional MAX phases.