A nanocrystalline Co-Cr-Ni-Fe compositional complex alloy (CCA) film with a thickness of about 1 micron was produced by a multiple-beam-sputtering physical vapor deposition (PVD) technique. The main advantage of this novel method is that it does not require alloy targets, but rather uses commercially pure metal sources. Another benefit of the application of this technique is that it produces compositional gradient samples on a disk surface with a wide range of elemental concentrations, enabling combinatorial analysis of CCA films. In this study, the variation of the phase composition, the microstructure (crystallite size and defect density), and the mechanical performance (hardness and elastic modulus) as a function of the chemical composition was studied in a combinatorial Co-Cr-Ni-Fe thin film sample that was produced on a surface of a disk with a diameter of about 10 cm. The spatial variation of the crystallite size and the density of lattice defects (e.g., dislocations and twin faults) were investigated by X-ray diffraction line profile analysis performed on the patterns taken by synchrotron radiation. The hardness and the elastic modulus were measured by the nanoindentation technique. It was found that a single-phase face-centered cubic (fcc) structure was formed for a wide range of chemical compositions. The microstructure was nanocrystalline with a crystallite size of 10–27 nm and contained a high lattice defect density. The hardness and the elastic modulus values measured for very different compositions were in the ranges of 8.4–11.8 and 182–239 GPa, respectively.