A quantitative proximity electron tunneling spectroscopy (PETS) is demonstrated for the study of strong coupling superconductors which do not form suitable insulating oxides for conventional McMillan-Rowell tunneling spectroscopy. Proximity junctions of the form C-AI203-AI/ S are employed, with A1 thickness d~r <-100 A. Here S is the superconductor of interest and C is any convenient counterelectrode. The physical basis for the method, experimental techniques, and data obtained from foils of Nb are presented. The results for Nb include the energy-dependent pair potential As(E), the renormalization function Z(E), effective phonon spectrum a 2F(to), electron-phonon coupling constant A, and Coulomb pseudopotential lz *. A full discussion of the underlying theory and details of the methods of analysis employed to obtain, in addition, the pair potential of the Al proximity layer are contained in a following paper.