•Densities were measured for the ethylene glycol (1) or glycerol (1) + hexane (2) or cyclohexane (2) or benzene (2) liquid systems at varying temperatures.•Volumetric properties were calculated using experimental data.•Intermolecular interactions were determed using volumetric properties.•Packing efficiency, πOH bonding, and dispersion forces were determined. The density values were measured as a function of mole fraction (ethylene glycol or glycerol for binary liquid systems such as ethylene glycol or glycerol + (hexane or cyclohexane or benzene at a temperature between 283.15 K and 328.15 K and atmospheric pressure. Using density data, the values of molar volumes, excess molar volume, and apparent molar volumes were calculated. Further, excess molar volume was correlated with the Redlich–Kister model. It is observed that in all systems, density data was decreased with an increase in the temperature and also increased with the concentration of ethylene glycol and glycerol. Excess molar volume for all the binary systems were positive deviations over the entire composition range. Each system exhibited more positive at a higher temperature. The obtained results are discussed in terms of packing efficiency, π−OH bonding, and dispersion forces. Display omitted