Theoretical calculations (usually density-functional-theory methods performed at 0 K) confirm the formerly assumed substitutional phosphorus segregation in α-iron. In contrast, the enthalpy-entropy compensation effect predicts that phosphorus should segregate interstitially. To resolve this discrepancy, we recalculated the values of the segregation enthalpy and entropy for the interstitial segregation of phosphorus according to the Guttmann model of segregation in multicomponent systems. This recalculation is based on earlier measured experimental data and shows that only slight changes in the values of the standard enthalpy and entropy of phosphorus, carbon and silicon segregation are obtained. Consequently, all dependences constructed previously remain qualitatively the same. By thermodynamic considerations based on the enthalpy-entropy compensation effect we quantitatively show that there is an alteration of the position of phosphorus at grain boundaries in α-Fe with increasing temperature: while substitutional segregation is preferred at 0 K, interstitial segregation occurs at temperatures of practical interest.