•The volumetric properties for ternary systems TMEDA/PMDETA + ACN + H2O and corresponding binary systems were investigated.•VmE, Vφ, V¯ and V¯E were all calculated.•VmE values for binary and ternary systems were all negative.•VmE values were correlated by R-K and N-T equations respectively. The densities of two ternary mixtures, N, N, N', N'-tetramethylethylenediamine (TMEDA) + acetonitrile (ACN) + H2O and pentamethyldiethylenetriamine (PMDETA) + ACN + H2O, and the corresponding binary mixtures TMEDA + ACN, PMDETA + ACN, TMEDA + H2O, PMDETA + H2O and ACN + H2O, were measured at different temperatures and 0.1 MPa. The studied temperatures are T = (288.15, 293.15, 298.15, 303.15, 308.15, 313.15, 318.15 and 323.15) K. From the experimental data, excess molar volume (VmE), apparent molar volume (Vφ), partial molar volume (V¯) and excess partial molar volume (V¯E), were calculated. Furthermore, the VmE values for the binary mixtures were fitted to the Redlich-Kister polynomial equation. For the ternary systems, the VmE values were fitted to Nagata-Tamura equation and the fitting results were compared with those by Cibulka, Singh and Redlich-Kister equations. All the results were analyzed from the intermolecular interactions and molecular structure.