Hybrid layered halide perovskites have achieved impressive performance in optoelectronics. New structural types in the two-dimensional (2D) halide system such as the Dion–Jacobson phases have attracted wide research attention due to the short interlayer distance and unique layer orientation that facilitate better charge-transport and higher stability in optoelectronic devices. Here, we report the first solid solution series incorporating both A and A’ cations in the 2D Dion–Jacobson family, with the general formula (A’)­(A)­Pb2Br7 ((A’ = 3-(aminomethyl)­piperidinium (3AMP) and 4-(aminomethyl)­piperidinium) (4AMP); A = methylammonium (MA) and formamidinium (FA)). Mixing the spacing A’ cations and perovskitizer A cations generates the new (3AMP) a (4AMP)1–a (FA) b (MA)1–b Pb2Br7 perovskites. The crystallographically refined crystal structures using single-crystal X-ray diffraction data reveal that the distortion of the inorganic framework is heavily influenced by the degree of A’ and A alloying. A rising fraction of 4AMP in the structure, decreases the Pb–Br–Pb angles, making the framework more distorted. On the contrary, higher FA fractions increase the Pb–Br–Pb angles. This structural evolution fine-tunes the optical properties where the larger the Pb–Br–Pb angle, the narrower the band gap. The photoluminescence emission energy mirrors this trend. Raman spectroscopy reveals a highly dynamical lattice similar to MAPbBr3 and consistent with the local distortion environment of the Pb2Br7 framework. Density functional theory (DFT) calculations of the electronic structures reveal the same trend as the experimental results where (3AMP)­(FA)­Pb2Br7 has the smallest band gap while (4AMP)­(MA)­Pb2Br7 has the largest band gap. The structural effects from solely the organic cations in the 2D system highlight the importance of understanding the high sensitivity of the optoelectronic properties on the structural tuning in this broad class of materials.