In this study, the cooling and dehumidification performance of a photovoltaic powered thermoelectric air conditioning system is investigated under tropical climate. The system is first investigated under a controlled environment with different flow arrangements of the hot junction cooling air stream. Better temperature reduction was observed when the cross-flow arrangement is used. Besides, it delivered the best reduction when 1.7 A current level is supplied to each thermoelectric module (TEM). The system performance was then investigated in a 3.6 m3 room application under real weather conditions. When 1.7 A current level supplied to each TEM, it delivered 181 W and 0.14 ltr/hour average cooling load and moisture removal rate, respectively. The corresponding indoor room temperature is 4 °C less than the unconditioned reference room, 7 to 7.6 °C lower than the outdoor in the afternoon, and the indoor relative humidity varies between 58 to 83%. The indoor thermal comfort analysis indicated that the indoor modified predicted mean vote is 0.24 and classified as Class A in the ISO thermal acceptability, coupled with 26.6% of mean dissatisfaction. Hence, the photovoltaic thermoelectric cooling system could be a potential option to substitute the conventional air conditioning system as it is Freon-free and no moving parts.