Overall, among these molecular spacers, it is anticipated that PEA-based quasi-2D film is the most suitable photoactive matrix. Despite notable chemical inhomogeneity, it can offer a stable and smooth film surface while minimizing the local phase inhomogeneity, which benefit PV performances and stability. In contrast, such an imperfect surface coverage of the crystallites in the DPA-based quasi-2D HP film is not expected to offer good charge transport features and PV performances, though the DPA indeed bestows excellent stability of the photoactive 3D-like phases.