The orientation of polymer chains plays an important role in governing the mechanical, optical, and electronic properties of polymeric materials. Here, we report on the fabrication of anisotropic polythiophene particles with controlled lengths using a metal–organic framework template, in which the alignment of the polymer chains was retained without a host support. The formation of the rod-shaped particles with long length allowed for the facile preferential orientation of the polymer particles, and consequently resulted in the macroscopic chain alignment of unprocessable polythiophene.