In a liquid chromatograph mass spectrometer (LC/MS) for performing mass spectrometry of fractionated samples prepared with a multi-dimensional LC or similar LC with high separatory capability, fractionated sample useful information which shows the degree of usefulness of various substances with respect to retention time is prepared from prior information which includes, for example, elution characteristics in the LC depending on the kind of column or other factors or the degree of ease of ionization in the MS. During a measurement, the preparative separation of an eluate and the preparation of fractionated samples are not performed within a period of time which has been judged to be useless based on the fractionated sample useful information. By selecting fractionated samples at each dimension of the multi-dimensional LC, the number of fractionated samples to be eventually subjected to mass spectrometry can be significantly reduced.