A new class of algorithms for the estimation of structural parameters of a continuous-time linear system excited by random natural disturbances is presented in the paper. All these algorithms are based on fitting the autocorrelation function of the system output; differences among arise from the various possible formulations of the fit-criterion. Thus, the asymptotic statistical properties of the estimate are analyzed in order to have a choice tool among the class of algorithms and to compare them with other existing estimation methods. A further relevant subject is the statement of an adaptive test to verify the correctness of the tentative model assumed for the sake of the estimation procedure. Then, the above algorithm is applied to the problem of estimating structural parameters (i.e. natural frequencies and damping factors) of the Italian and Yugoslavian power systems by recording some main electrical quantities during the normal operation of the system. Capability of dealing with structural systems affected by an unknown number of oscillation modes and simplicity of use by non-statistical people are interesting features of the present approach, emphasized by the application.