We have grown Bi1-xSbx alloy thin films on CdTe(111)B over a wide range of Sb concentrations (0≤x≤0.183) using MBE. We have observed several differences with the bulk system. The 3.5 and 5.1% Sb alloys show semiconducting behavior, and the Sb concentration with the maximum bandgap is shifted to a lower Sb concentration, from 15% in bulk to 9%. The power factor S2/ρ (where S is thermoelectric power(TEP) and ρ electrical resistivity) peaks at a significantly higher temperature (250K) than previously reported for the bulk alloy (80K). The magnetotransport properties of Bi1-x,Sbx thin films (x = 0, 0.09, and 0.16) and Bi/CdTe superlattices have been determined by applying the Quantitative Mobility Spectrum Analysis (QMSA) and multicarrier fitting to the magneticfield- dependent resistivities and Hall coefficients, using algorithms which account for the strong anisotropy of the mobilities. The calculated S values are in good agreement with experimental results. The structural stability of bulk Bi is studied using the local density linear muffin-tin orbital method. It is shown that the internal displacement changes the Bi electronic structure from a metal to a semimetal, in qualitative agreement with a Jones-Peierls-type transition. The total energy is calculated to have a double well dependence on the internal displacement, and to provide a stabilization of the trigonal phase. We show that an increase of the trigonal shear angle leads to a semimetal-semiconductor transition in Bi.