2D materials, particularly those bearing in‐plane anisotropic optical and electrical properties such as black phosphorus and ReS₂, have spurred great research interest very recently as promising building blocks for future electronics. However, current progress is limited to layered compounds that feature atomic arrangement asymmetry within the covalently bonded planes. Herein, a series of highly anisotropic nanosheets (Sb₂Se₃, Sb₂S₃, Bi₂S₃, and Sb₂(S, Se)₃), which are composed of 1D covalently linked ribbons stacked together via van der Waals force, is introduced as a new member to the anisotropic 2D material family. These unique anisotropic nanosheets are successfully fabricated from their polymer‐like bulk counterparts through a gentle water freezing‐thawing approach. Angle‐resolved polarized Raman spectroscopy characterization confirms the strong in‐plane asymmetry of Sb₂Se₃ nanosheets, and photodetection study reveals their high responsivity and anisotropic in‐plane transport. This work can enlighten the synthesis and application of new anisotropic 2D nanosheets that can be potentially applied for future electronic and optoelectronic devices.