Reduced-dimensional perovskites (RDPs) have advanced the development of perovskite solar cells (PSCs) due to their tunable energy landscape, structure, and orientation. Thus, we aim for an increase in the understanding of structure-photophysical properties of Dion-Jacobson (DJ) and Ruddlesden-Popper (RP) RDPs with different dimensionalities. Our findings reveal that RP RDPs with lower dimensionality exhibits a dominant n=2 phase, preferential out-of-plane orientation, and longer charge carrier lifetime compared with DJ RDPs, as evidenced by X-ray scattering technique and transient absorption spectroscopy. In addition, we unveil the film growth of respective RDPs by in-situ X-ray scattering, showing the stoichiometry-determined phase growth. The formation of lower-n phases in RP RDPs with higher dimensionality is thermodynamically favored, while those phases are likely in the form of “intermediate phase”, which bridge the 3d-like and lower-n phases in DJ RDPs. DJ RDPs with higher dimensionality demonstrate comparable phase purity, giving rise to more sufficient energy transfer and longer charge carrier lifetime. As such, DJ-based PSCs (n=4) demonstrate better device stability under ISOS-I-L conditions compared to RP-based PSCs. Leveraging these structural and photophysical insights, our work paves the way for dictating the utilization of RDPs in 3D PSCs and the fabrication of quasi-2D solar cells.