Two-dimensional Ruddlesden-Popper perovskites (2D RPPs) have been considered as promising building blocks for optoelectronic applications owing to optical properties comparable to the ones of 3D perovskites, together with superior stability. In addition, the more flexible structure adopted by such perovskites leads to a relaxation of the Goldschmidt tolerance factor (tau) requirement. Herein, we compare the crystalline and electronic structures, as well as the photophysics of two 2D perovskite single crystals (n-BA)(2)(MA)(2)Pb3I10 (BMAPI) and (n-BA)(2)(EA)(2)Pb3I10 (BEAPI) (n-BA = n-butylamine) containing small A-cations (MA, methylammonium) and large A-cations (EA, ethylammonium), respectively. The latter presents a relaxed tau (tau(EA) > 1) compared with the requirement of a stable phase in 3D perovskites (tau <1). Such relaxed t is beneficial from the structural flexibility of the long organic cation bilayer and the pronounced lattice distortions in the 2D perovskite structures. We further elucidate how the greater lattice distortions concurrently modulate the electronic structure as well as trap densities in these 2D RPPs. The electronic band gap (E-g) of BEAPI (2.08 +/- 0.03 eV) is similar to 0.17 eV larger than the one of BMAPI (1.91 +/- 0.03 eV). This is mainly because of a shift in the valence band maximum associated with the expansion of the Pb-I bond length in BEAPI. In addition, the overall trap state densities for BMAPI and BEAPI are calculated to be similar to 2.18 x 10(16) and similar to 3.76 x 10(16) cm(-3), respectively, as extracted from the time-resolved photoluminescence studies. The larger trap density in BEAPI can be attributed to the stronger interfacial lattice distortion that sets in when large EA cations are contained into the inorganic crystal lattice.