Understanding the photocurrent transportation within porphyrin-containing metal–organic frameworks (PMOFs) will be a critical step in applying these materials in light-harvesting molecular devices in the future. Two copper porphyrin paddle-wheel frameworks (Cu-PPFs) were employed to study the influence of metal ions coordinated into the porphyrin ligands on conductivity and photoelectron transfer capability. To compare the electronic and optical properties of both materials, we prepared an ultrathin film of each PPF via a Langmuir–Blodgett method. The resulting films exhibited uniform morphology and single-crystalline domains, in addition to photoelectric conversion capabilities. We confirmed that both Cu-PPFs have semiconducting properties with an optical band gap of around 2.7 eV. The current density generated by both Cu-PPFs was studied through a mercury drop junction approach. We observed a slightly higher conductivity from the Cu-PPF film consisting of metalloporphyrins than the one without copper doping in the porphyrin centers. In addition, the copper-ion-coordinated porphyrins were found to be more favorable for facilitating photoinduced electron transfer from the Cu-PPF film to a conductive glass substrate. This work presents a new approach of combining thin film fabrication and electro-heterojunction measurement to study electron transfer within an ultrathin film.