Molar excess volumes, VE, and molar excess enthalpies, HE, have been measured for acetone (A) + bromoform (B) mixtures at 298.15 and 308.15 K. Results of these measurements suggest the formation of a 1:1 acetone–bromoform molecular complex. The equilibrium constant, K, the enthalpy of formation, ΔH, of the AB complex as also the molar volume change, ΔV, accompanying the complexation reaction [Formula: see text] have been evaluated from the measured HE and VE data. The K value so obtained has further been substantiated by the K value determined for the AB molecular entity from nmr studies on this mixture. Partial molar enthalpy of B (at infinite dilution) in A and vice versa have also been evaluated from the measured HE data at 298.15 K and used to calculate a consistent molar enthalpy of AB complex formation.