In accordance with the International Standard Organization ISO 17043, two proficiency tests (PTs) for the simultaneous determination of aflatoxins (AFB1, AFB2, AFG1, AFG2); deoxynivalenol; fumonisins FB1, FB2, and B3; ochratoxin A, the T-2 toxin; and the HT-2 toxin were conducted in 2019 and 2020 using cornflakes and rusk flours that were prepared in house. The homogeneity and the stability of these materials were verified according to the criteria laid down in ISO 13528 using randomly selected samples. Most of the targeted toxins were found to be homogenously distributed in both materials with no significant changes during the timescale of the PTs. Next, the materials were distributed to approximately 25 participating laboratories from Europe, Canada, and the United States. The obtained datasets were computed using robust statistics. The outliers were checked and removed, and the toxin concentrations were assigned as the consensus value of the results of the participants at Horwitz ratios <1.2. The z scores were generated for all mycotoxins, and the results were pooled to calculate the relative sum of squared z scores (SZ2) indexes and were clustered according to the triple A rating. Overall, at least 80% of the participating laboratories achieved good and acceptable performances. The most frequent categories assigned to good performances (SZ2 ≤ 2) were AAA (51%) and BAA (13%). Clusters of BBA + CBA (6%) included laboratories reporting acceptable z scores <90% of the total z scores for less than 90% or 50% of the mycotoxins targeted in the 2 matrices. The triple A rating seems to be appropriate in evaluating the performances of laboratories involved in multi-mycotoxin analyses. Accredited and non-accredited analytical methods achieved good and acceptable performances.