Edible mushrooms have been recognized as a highly nutritional food for a long time, thanks to their specific flavor and texture, as well as their therapeutic effects. This study proposes a new, simple approach based on FT-IR analysis, followed by statistical methods, in order to differentiate three wild mushroom species from Romanian spontaneous flora, namely, Armillaria mellea, Boletus edulis, and Cantharellus cibarius. The preliminary data treatment consisted of data set reduction with principal component analysis (PCA), which provided scores for the next methods. Linear discriminant analysis (LDA) managed to classify 100% of the three species, and the cross-validation step of the method returned 97.4% of correctly classified samples. Only one A. mellea sample overlapped on the B. edulis group. When kNN was used in the same manner as LDA, the overall percent of correctly classified samples from the training step was 86.21%, while for the holdout set, the percent rose to 94.74%. The lower values obtained for the training set were due to one C. cibarius sample, two B. edulis, and five A. mellea, which were placed to other species. In any case, for the holdout sample set, only one sample from B. edulis was misclassified. The fuzzy c-means clustering (FCM) analysis successfully classified the investigated mushroom samples according to their species, meaning that, in every partition, the predominant species had the biggest DOMs, while samples belonging to other species had lower DOMs.