In this work, calcium fluoride (CaF2) and Tb3+-doped calcium fluoride (CaF2:Tb3+) thin films were prepared by electrochemical methods. According to EDS and XRD results, CaF2 thin films undergo through a phase transformation from cubic CaF2:Tb3+ to NaTbF4 when Tb3+ concentration in the electrolytic bath is increased. So that, peaks showed a very clear shifting towards lower angles. On the other hand, optical absorption results showed the typical range of transparency from IR to UV, and from photoluminescence (PL) spectra results it can be observed that it is possible to identify the f-f transition of Tb3+. The PL at low temperature allows finding the quenching concentration when the PL intensity decreases at the highest doping concentration value. However, the results also showed that the transition of Tb3+ does not seem to be affected by the coexistence of the secondary phases such as cubic NaTbF4. In the case of RE-doped CaF2 thin films materials, they can be used with a double purpose for solar cell applications, not only as antireflecting coating, but also as a host for lanthanide doping for down conversion of light. These properties could be very useful for photovoltaic applications, so that the spectral range of light conversion could be increased to achieve higher conversion efficiency values.