Metal/CaF2/p-Si(111) capacitors with the improved-quality several-nanometer-thick epitaxial fluorite films are examined, aiming at solidifying a candidacy of this material for barrier layers in silicon devices. Structural and transport properties of a thin crystalline dielectric are characterized by different experimental techniques. The measured current-voltage characteristics accompanied with simulation results demonstrate that the elastic tunneling electron injection takes place in the considered structures. The same result follows from the behavior of hot-electron-injection-related electroluminescence within the selected spectral intervals. The result is important considering a perspective of using the epitaxial fluorides as barrier layers in resonant tunneling diodes.