This paper presents the results of thermodynamics modelling studies of a 2 kW (e) biomass-fired CHP system with organic Rankine cycle (ORC). Three environmentally friendly refrigerants, namely HFE7000, HFE7100 and n-pentane, have been selected as the ORC fluids. The thermodynamic properties of the selected ORC fluids which have been predicted by commercial software (EES) are used to predict the thermal efficiency of ORC. The results of modelling show that under the simulated conditions (1) the ORC thermal efficiency with any selected ORC fluid is well below (roughly about 60% of) the Carnot cycle efficiency; the ORC efficiency depends on not only the modelling conditions but also the ORC fluid the highest predicted ORC efficiency is 16.6%; the predicted ORC efficiency follows the following order: n-pentane > HFE7000 > HFE7100 (2) both superheating and sub-cooling are detrimental to the ORC efficiency (3) the electrical efficiency of the CHP system with the selected ORC fluids is predicted to be within the range of 7.5%-13.5%, mainly depending on the hot water temperature of the biomass boiler and the ORC condenser cooling water temperature as well as the ORC fluid, and corresponding to about 1.5 kW and 2.71 kW electricity output (4) the overall CHP efficiency of the CHP system is in the order of 80% for all three ORC fluids although the amount and quality of heating supplied by the CHP system depend on the ORC fluid selected and the modelling conditions. (C) 2011 Elsevier Ltd. All rights reserved.