A method has been developed for the preparation of alloy preparations suitable directly, without further mechanical treatment, for measuring electrical conductivity; this is especially important for brittle and easily oxidized alloys. The electrical conductivity and its temperature coefficient were measured for five alloy systems with clearly defined compounds, the nature of which was precisely established, by means of various metallographic methods. Existing theories of electrical conductivity of alloys are analyzed. An attempt has been made to theoretically explain the differences in the properties of the temperature coefficient of certain compounds and solid solutions, which are not provided by the existing theories.