Nonspherical anisotropic particles, as basic building blocks, have been catching much attention in recent decades. However, it is still a challenge to produce nonspherical particles by traditional approaches. Here, we reported a facile method to fabricate hexagonal particles via the double solvent swelling method. When the crystal arrays were immersed in the double -solvent system of N,N-dimethylformamide (DMF) and tetraethyl orthosilicate (TEOS), the particles were swollen and squeezed into hexagonal particles. The concave size of hexagonal particles was controlled by tuning the mass ratio of the solvent and the swelling time. In addition, the particles with novel morphology were also prepared by swelling the arrays with a distinct lattice structure. The monodispersed particle possesses a well-defined hexagonal morphology and the liquid crystal phenomenon, which has promising applications in the fields of photonics, optical devices, and toners.