A total reflection X-ray fluorescence method was developed to ascertain the absence of indium at a concentration level of >1 ng/mL in heavy water samples. A continuum strip in the energy range of 25–35 keV was used for sample excitation and In Kα was used as analytical line. The detection limit for indium, obtained after preconcentration and continuum excitation, was found to be 1 ng/mL with a sample size of 2μL. A heavy water sample was analysed for indium using this approach.