The current-voltage (I-V) characteristics of single-barrier and double-barrier tunneling diode structures using CaF 2 /CdF 2 /Si ultrathin multilayered heterostructures grown on Si substrates have been theoretically analyzed and their material parameters, such as the conduction band discontinuity (ΔE C ) at the heterointerface and effective mass (m » ), have been evaluated by fitting simulation with the measured I-V characteristics. ΔE C between the ultrathin (1-3 nm) CaF 2 and Si layers and m » for CaF 2 were found to be 1.5-2.3 eV and 0.3-1.0m 0 , respectively. A clear thickness dependence of these parameters was observed, and the deviations of m » and ΔE C were approximately 30-50%, which probably originated from the thin layer thicknesses in atomic order. Using the estimated values derived from the single-barrier tunneling diodes, m » for CdF 2 was also estimated to be 0.36m 0 by fitting simulation of double-barrier diodes. These results will contribute to clarifying the design principle of tunneling devices with CaF 2 and enhancing quantitative studies on electron transport in atomically thin multilayered heterostructures.