Low-dimensional halide perovskites have recently attracted intense interest as alternatives to the three-dimensional (3D) perovskites because of their greater tunability and higher environmental stability. Herein, we present the new homologous 2D series (NH3C mH2 mNH3)(CH3NH3) n-1Pb nI3 n+1 ( m = 4-9; n = 1-4), where m represents the carbon-chain number and n equals layer-thickness number. Multilayer ( n > 1) 2D perovskites incorporating diammonium cations were successfully synthesized by the solid-state grinding method for m = 4 and 6 and by the solution method for m = 7-9. Structural characterization by single-crystal X-ray diffraction for the m = 8 and m = 9 series ( n = 1-4) reveals that these compounds adopt the Cc space group for even n members and Pc for odd n members. The optical bandgaps are 2.15 eV for two-layer ( n = 2), 2.01 eV for three-layer ( n = 3), and 1.90 eV for four-layer ( n = 4). The materials exhibit excellent solution processability, and casting thin-films of the n = 3 members was successfully accomplished. The films show a clear tendency for the higher- m members to have preferred orientation on the glass substrate, with m = 8 exhibiting almost perfect vertical layer orientation and m = 9 displaying both vertical and parallel layer orientation, as confirmed by grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements. The vertical layer orientation for the (NH3C8H16NH3)(CH3NH3)2Pb3I10 member results in the best thermal, light, and air stability within this series, thus showing excellent potential for solar cell applications.