As part of a study of ion migration mechanisms in feldspars, the dynamical behaviour of the alkali metal cations ions in albite and K-feldspar has been investigated using a combination of dielectric spectroscopy and atomistic computer simulation techniques. The low-frequency dielectric properties of these minerals have been studied from room temperature to 1100 K. At each temperature, the dielectric constant, conductivity and dielectric loss were determined over a range of frequencies from 100 Hz to 10 MHz. At high temperatures a distinct Debye-type relaxation in the dielectric loss spectra was observed for both albite and K-feldspar; the activation energy for these processes was determined to be 1.33 eV in both albite and K-feldspar. Atomistic simulation techniques were used to elucidate the mechanism and energetics of the cation migration processes. Mechanisms involving the conventional hopping of Na+ and K+ ions between cation sites in the (010) plane were found to give calculated energy barriers in good agreement with the experimentally determined activation energies. These results assist in understanding the nature of the processes responsible for the observed dielectric behaviour.