The taking of samples is a very important stage in the process of preparing representative material for tests and obtaining reliable test results. The laboratories that strive for high quality of the services they offer should monitor their test results against the background of the results obtained by other reputable laboratories that provide similar services. In the pursuing of this objective, an excellent tool is the proficiency testing, which makes it possible to confirm the competence of laboratories to carry out fuel tests and/or to take fuel samples. The Automotive Industry Institute (PIMOT), as a leading body engaged in Poland in examining the quality of the propane-butane gas (LPG) used as a fuel, organized tests of the proficiency at taking LPG samples from a dispenser at a filling station. The tests were carried out for a number of laboratories that provided services within a similar scope. The laboratories participating in this project took fuel samples and sent them to the organizer for the samples to be tested and for the method of taking the LPG samples to be verified. In the article, the importance of taking the samples and of participating in the tests of proficiency at taking samples of liquefied propane-butane gas has been presented, the method of preparing representative material for tests and of verifying the homogeneity and stability of the batch under test has been described, and the approach to the examination of proficiency at taking LPG samples from a dispenser at a filling station has been discussed. The proficiency test results obtained from the participants have been presented, discussed, and analysed.