Volume diffusion of 14C in high purity α‐Fe single crystals is measured in the wide temperature range of 1168 to 596 K applying the radiotracer technique and serial sectioning of the samples. In the temperature range in which the present tracer and previous Snoek‐effect measurements overlap a good agreement is found between the directly and indirectly measured diffusion coefficients. From this it is concluded that in the whole temperature range C‐atoms diffuse interstitially only via octahedral sites in α‐Fe. The data reveal a dependence on temperature which is typical for the influence of the magnetic phase transition on diffusion. The interstitial C diffusion responds more strongly to the stiffening of the lattice, which is related to the magnetic ordering, than the vacancy mediated self‐diffusion. Grain boundary diffusion of C in α‐Fe is observed below 740 K. The evaluation of the diffusion profiles results in Pc = sδD gbC which is 8 to 9 orders of magnitude larger than PFe = δD gbFe measured for grain boundary self‐diffusion in the same Fe‐material. Taking into account the segregation coefficient s, the still large difference between D gbC and D gbFe leads to the conclusion that C diffuses interstitially also in α‐Fe grain boundaries.