The use of accelerator mass spectrometry (AMS) for age determinations of paintings is growing due to decreasing sample size requirements. However, as only the support material is usually dated, the validity of the results may be questioned. This work describes a novel sampling and preparation technique for dating the natural organic binder using radiocarbon (14C) AMS. In the particular case of oil paintings, the natural oil used has a high probability of being representative of the time of creation, hereby circumventing the problem of the originality of the support material. A multi-technique approach was developed for a detailed characterization of all paint components to identify the binder type as well as pigments and additives present in the sample. The technique was showcased on a painting of the 20th century. The results by 14C AMS dating show that both the canvas and binding medium predate the signed date by 4–5 yr. This could be the time span for keeping painting material in the atelier. The method developed provides, especially given the low amounts of material needed for analysis, a superior precision and accuracy in dating and has potential to become a standard method for oil painting dating.