Successive dilution enthalpies (Delta H(m(N-1) -> m(N))) of glycidol enantiomers (R-(+)-glycidol, S-(-)-glycidol) and the racemate (R/S-(+/-)-glycidol) in (dimethylformamide (DMF) + water) mixtures rich in water (mass fractions of DMF, w(DMF) = 0 to 0.25) have been determined respectively by isothermal titration calorimetry (ITC) at T = 298.15 K. The corresponding homotactic enthalpic pairwise interaction coefficients (h(XX)) of each compound have been evaluated from the framework of McMillan-Mayer theory. Across the studied composition range of (DMF + water) mixtures the h(XX) values of these compounds are all positive, and decrease gradually with the mass fraction of DMF by the order hRR > hRS approximate to hMM > hSS > 0 (M represents the racemate R/S-(+/-)-glycidol, and h(RS) is the estimated value for the heterochiral pair R-S). The positive values of h(XX) indicate that pairwise interactions of these compounds are endothermic and unfavourable from the point of view of enthalpy. The interaction of S-S pair is considered to be slightly stronger than M-M, R-S and R-R pairs since the former absorbs less heat than the latter in pairwise interactions. The addition of cosolvent (DMF) is in favour of pairwise interactions of these compounds in the mixtures rich in water. (C) 2015 Elsevier Ltd. All rights reserved.