The equilibrium and transport properties of mixtures of two ionic liquids – [C4C1Im][OAc] and [C4C1Im][C(CN)3] – were determined and interpreted at the molecular level using vibration spectroscopy, NMR and molecular dynamics simulation. The non-ideality of the mixtures [C4C1Im][OAc](1−x)[C(CN)3]x was characterized by VE = +0.28 cm3 mol−1 (293 K, x = 0.65) and HE = −2.2 kJ mol−1 for x = 0.5. These values could be explained by a rearrangement of the hydrogen-bond network of the mixture that favours the interaction of the acetate anion with the imidazolium cation at position C2. The dynamic properties of the mixture are also dramatically influenced by the composition with a decrease of the viscosity and an increase of self-diffusion coefficients of the ions when the amount of tricyanomethanide anion increases in the mixture.