CuFeO<SUB>2</SUB> is a narrow band gap oxide semiconductor that can be p- or n-type and can absorb visible light. Therefore, delafossite CuFeO<SUB>2</SUB> is interesting for photovoltaic applications. Here, the fabrication and characterization of delafossite p-n junctions, consisting of p-type Cu(Fe,Mg)O<SUB>2</SUB> and n-type Cu(Fe,Sn)O<SUB>2</SUB>, are reported. Cu(Fe,Sn,Mg)O<SUB>2</SUB> substrates and targets were synthesized by solid-state reaction. Delafossite Cu(Fe,Sn,Mg)O<SUB>2</SUB> films were grown by pulsed laser deposition (PLD) on either polycrystalline doped CuFeO<SUB>2</SUB> substrates or as heterojunctions on YSZ (100) single crystals. The structure of delafossite substrates and films on YSZ were investigated by X-ray diffraction (XRD), while the delafossite films on the polycrystalline substrates were examined by electron backscatter diffraction (EBSD). I-V characteristics were measured to understand the electrical performance of the materials. A comparison of the electrical properties of both p-n junction structures will be discussed, as will the applicability of CuFeO<SUB>2</SUB> in photovoltaic applications.