The breaking of inversion symmetry can enhance the multifunctional properties of layered hybrid organic–inorganic perovskites. However, the mechanisms by which inversion symmetry can be broken are not well-understood. Here, we study a series of MnCl 4 -based 2D perovskites with arylamine cations, namely, (C 6 H 5 C x H 2 x NH 3 ) 2 MnCl 4 ( x = 0, 1, 2, 3), for which the x = 0, 1, and 3 members are reported for the first time. The compounds with x = 1, 2, and 3 adopt polar crystal structures to well above room temperature. We argue that the inversion symmetry breaking in these compounds is related to the rotational degree of freedom of the organic cations, which determine the hydrogen bonding pattern that links the organic and inorganic layers. We show that the tilting of MnCl 6 octahedra is not the primary mechanism involved in inversion symmetry breaking in these materials. All four compounds show 2D Heisenberg antiferromagnetic behavior. A ferromagnetic component develops in each case below the long-range magnetic ordering temperature of ∼42–46 K due to spin canting.