Multiple features strongly associated with the chemistry of spacer cations were identified. It is found that the use of a spacer with phenyl rings manifests stable 3Dlike phases -high-n 2D HP structures where the surface coordinated spacers protect 3D CsPbI3 lattice, which is failed to realize by employing thiophene ring or short alkyl chain spacers. This allows for the construction of stable HP film matrices that render an optimal bandgap of ~1.8 eV. Such discrepancy is likely attributed to the difference in geometric symmetry for spacer-precursor chemical interaction. Note that the HP matrix with bulky DPA offers uneven surface morphology with segmented 3D-like HP crystallites compromising charge transport upon device application, though it exhibits outstanding phase stability . Additionally, in contrast to the Ruddlesden-Popper (RP) type HPs that typically render severe 2D/3D phase separation along the vertical direction , incorporation of Dion-Jacobson (DJ) type perovskite (i.e., BDAPbI4) homogenizes the vertical phase distributions. These observations collectively reveal the importance of spacer chemistry for synthesizing quasi-2D HP matrices.