Porphyrins bearing bulky alkoxyphenyl substituents at two of the four meso-positions and phenyl phosphonates at the other two have been prepared and used as building blocks for layer-by-layer assembly of conductive-glass-supported thin films via zirconium phosphonate chemistry. Thin-film characterization shows that the addition of sterically demanding 2,6-di(n-hexoxy)phenyl substituents to the meso-positions of the porphyrin skeleton can successfully prevent molecular aggregation. Both absorption and emission studies of multilayer thin films provide strong evidence that the new compounds have the ability to form thin films in which very little molecular (chromophore) interaction is present, relative to porphyrins that are not sterically hindered. Furthermore, the films are found to be permeable to selected small redox probes but blocking toward larger ones. Taken together, the sharp absorption spectra, increased emission yields, and permeability are expected to be advantageous for various materials-based applications such as photovoltaics and sensors.