Thermoelectric (TE) modules are possible reversible pre-cooling and pre-heating devices for ventilation air in buildings. In this study, the opportunity of direct coupling of TE modules with photovoltaic (PV) cells is considered. This coupling is evaluated through a numerical simulation depending on the meteorological conditions of Chambery, Alpine region in France, and on the cooling or heating use of the TE modules, through annual energy and exergy efficiencies. For the considered conditions, TE module performances are of the same order as the ones of the vapour compression heat pumps, with a TE coefficient of performance higher than 2 for low values of input DC current. The PV TE coupling efficiency varies between 0.096 and 0.23 over the year, with an average value of 0.157. Evolutions of the exergy effectiveness of PV and TE elements follow the same trends as the corresponding energy efficiencies but with steeper variations for the coupling exergy yield that varies between 0.004 and 0.014, with an annual average value of 0.010. The direct PV-TE coupling does not seem to be a sustainable option for the summer cooling purpose particularly. A case study with indirect coupling under a warm climate is considered and shows that the use of TE devices could be efficient in housing to ensure summer thermal comfort, but the corresponding necessary PV area would induce a high investment. Copyright (c) 2008 John Wiley & Sons, Ltd.