A new method for determining isobaric thermal expansivity of liquids as a function of temperature and pressure through calorimetric measurements against pressure is described. It is based on a previously reported measurement technique, but due to the different kind of calorimeter and experimental set LIP, a new calibration procedure was developed. Two isobaric thermal expansivity, standards are needed; in this work, with a view on the quality of the available literature data, hexane and water are chosen. The measurements were carried out in the temperature and pressure intervals (278.15 to 348.15) K and (0.5 to 55) MPa for a set of liquids, and experimental values are compared with the available literature data in order to evaluate the precision of the experimental procedure. The analysis of the results reveals that the proposed methodology is highly accurate for isobaric thermal expansivity, determination, and it allows obtaining a precise characterisation of the temperature and pressure dependence of this thermodynamic coefficient. (C) 2008 Elsevier Ltd. All rights reserved.