Transport properties of superionic conductors with a tysonite-type structure have been investigated by impedance spectroscopy, ¹⁹F NMR, high hydrostatic pressure and radio tracer (³⁶Cl) techniques. It is demonstrated that these experimental methods are powerful tools to clarify ionic processes on the microscopic level in investigated solid electrolytes with predominant fluorine mobility. Correlation between transport properties and structural data were established.