Relative permittivities at 1 MHz, epsilon r, and at (293.15-303.15) K, are reported for the binary systems N,N-dimethylformamide (DMF) + N-propylpropan-l-amine (DPA), +N-butylbutan-l-amine (DBA), + butan-1amine (BA) or +hexan-l-amine (HxA). The values of the excess relative permittivities, 4, have also been determined for these solutions. The measurements were realized by means of a precision impedance analyser 4294A, to which a 16452A cell connected using a 16048G test lead, all of them from Agilent. The 4 values are large and negative, and diminish when the size of the amine increases along a homologous series, which has been ascribed mainly to the rupture of interactions between like molecules along mixing. Calculations on excess molar orientational polarizabilities support this conclusion, indicating a dominant contribution to epsilon(E)(r) from the orientational polarizability of the molecules in the mixture. The analysis of excess relative Kirkwood correlation factors shows that the correlation between dipoles is effectively decreased along the mixing process. (C) 2017 Elsevier B.V. All rights reserved.