In order to demonstrate the usefulness of alpha-particle activation analysis, simultaneous determination of P, Cl, K and Ca in commercially available control serums has been studied fundamentally. After thick target yield curves of radionuclides produced from the element to be determined were measured as a function of alpha energy together with those of the interferences, an optimum working standard for the present experiments was provided by applying the internal standard method to a human serum under the most suitable bombardment conditions. Then, the concentrations of the above four elements in several control serums were determined efficiently and reasonably by ordinary alpha-particle activation analysis.