A method for analyzing a sample containing a plurality of substances, having the following steps: - receiving mass spectra (mass spectra data D) of the sample obtained from an upstream chromatograph in a measurement device, - assigning chromatograph peaks (a) and (b) and their corresponding mass spectra to one of the substances in each case, wherein the assignment is made in a first evaluation device and/or a second evaluation device, wherein the first evaluation device has at least one comparison device for comparing deconvoluted mass spectra with stored reference spectra and the second evaluation device has at least one comparison device for comparing mass spectra of the chromatographic peaks of the ions with stored reference spectra, - wherein the step of assigning in the first evaluation device comprises the deconvoluting of the mass spectra obtained from the measurement device and the assigning of the chromatographic peaks (a) and their corresponding deconvoluted mass spectra to one of the substances in each case on the basis of the match with a reference spectrum of the substance, and - wherein the step of assigning in the second evaluation device comprises the ascertaining of the intensity of the peaks of the ions of the mass spectra obtained from the measurement device with specification of ions specific to the substance and their retention time range, and the assigning of the chromatographic peaks (b) of the ions and their corresponding mass spectra to one of the substances in each case on the basis of the match of selective ions and their retention time ranges of the peaks (b) with the reference values fixed for a substance, and - verifying the assignments made in the first and/or second evaluation device (A, B) in a validation device at least using peak-oriented rules, wherein the validation device, when the first and/or second evaluation unit (A, B) is used, verifies - whether the retention index of a peak (a or b) assigned to a substance by the evaluation device (A, B) is within defined limits (rules P15, PB) and - that a peak (a or b) found by the first and/or second evaluation device (A, B) and optionally assigned to a substance has not been standardized to a standard peak that is absent or has not been successfully verified by rules implemented and activated beforehand (rule P20), only the peaks of the evaluated or deconvoluted mass spectra signals that have each been successfully verified by activated rules are approved for further evaluation, and wherein it is verified in parallel whether a sample that has been fractionated prior to the analysis has peaks in fractions marked as absent or as incorrect measurements, and excluding such peaks from further analysis (rule S2), and issuing a warning message if no peaks are found for a fraction present (rule CP1). - receiving mass spectra (mass spectra data D) of the sample obtained from an upstream chromatograph in a measurement device, - assigning chromatograph peaks (a) and (b) and their corresponding mass spectra to one of the substances in each case, wherein the assignment is made in a first evaluation device and/or a second evaluation device, wherein the first evaluation device has at least one comparison device for comparing deconvoluted mass spectra with stored reference spectra and the second evaluation device has at least one comparison device for comparing mass spectra of the chromatographic peaks of the ions with stored reference spectra, - wherein the step of assigning in the first evaluation device comprises the deconvoluting of the mass spectra obtained from the measurement device and the assigning of the chromatographic peaks (a) and their corresponding deconvoluted mass spectra to one of the substances in each case on the basis of the match with a reference spectrum of the substance, and - wherein the step of assigning in the second evaluation device comprises the ascertaining of the intensity of the peaks of the ions of the mass spectra obtained from the measurement device with specification of ions specific to the substance and their retention time range, and the assigning of the chromatographic peaks (b) of the ions and their corresponding mass spectra to one of the substances in each case on the basis of the match of selective ions and their retention time ranges of the peaks (b) with the reference values fixed for a substance, and - verifying the assignments made in the first and/or second evaluation device (A, B) in a validation device at least using peak-oriented rules, - whether the retention index of a peak (a or b) assigned to a substance by the evaluation device (A, B) is within defined limits (rules P15, PB) and - that a peak (a or b) found by the first and/or second evaluation device (A, B) and optionally assigned to a substance has not been standardized to a standard peak that is absent or has not been successfully verified by rules implemented and activated beforehand (rule P20),