Abstract A solvent free, fast and environmentally friendly photoacoustic-infrared-based methodology (PAS-FTIR) was developed for the determination of Mancozeb in agrochemicals. This methodology was based on the direct measurement of the transmittance spectra of solid samples and a multivariate calibration model to determine the active ingredient concentration. The proposed partial least squares (PLS) model was made using nine standards prepared by mixing different amounts of kaolin and Mancozeb, with concentrations between 5.43 and 88.10% (w/w). A hierarchical cluster analysis was made in order to classify the samples in terms of similarity in the PAS-FTIR spectra. From their spectra different commercially available fungicide samples were classified in four groups, attending to the presence of other active ingredients co-formulated with Mancozeb. Different PLS models were applied for the analysis of each group of samples. So, for samples containing copper oxychloride (group 1), the information in the spectral range from 1543 to 1474 and 1390 to 1269 cm −1 was employed. For samples co-formulated with Fosetyl-Al (group 2) the range between 3334 and 3211 cm −1 , corrected with a single point baseline located at 3055 cm −1 , was used. For samples containing Metalaxyl (group 3) it was used the information in the spectral range from 1543 to 1474 cm −1 was used to determine Mancozeb. Finally, the range between 1456 and 1306 cm −1 was used for Mancozeb determination in samples containing Cymoxanil (group 4). The PLS factors used for Mancozeb determination depends on the PLS model employed. 3, 2, 2 and 3 factors were used for Mancozeb determination in commercially available pesticides for groups 1, 2, 3 and 4, respectively. The mean accuracy errors found were 3.1, 2.1, 2.5 and 3.0% for groups 1, 2, 3 and 4, respectively. The developed PAS-FTIR methodology does not consume any solvent, as no sample preparation is necessary it improves the laboratory efficiency without sacrifice the accuracy and avoids the contact of the operator with toxic substances.