Proficiency testing (PT) allows food laboratories to endorse their competency to provide food safety guarantees to producers and consumers. One of the recommended methods for assigning reference values in PT with a small number of participants consists in considering the results that a laboratory obtains by means of a calibration test based on certified reference material (CRM). The present study delves into the results from eight PT rounds on the determination of fat and crude protein from raw milk, with modifications in the number of samples and the analysis sessions from that required by the ISO 13528:2022. The uncertainty criterion of the assigned value established by the ISO 13528:2022 standard was met by 93% of the participating laboratories, which allowed most participants to be evaluated through z-score. The assigned values were generally compatible with the results obtained by the participants. Thus, it can be concluded that the design for the assignment of the reference value is appropriate for PT with a limited number of participants. It is recommended for future PT to limit the uncertainty of the CRM according to their availability and to update the standard deviation of the proficiency assessment for the Mid-Infrared Spectroscopy method (MIR).