A total reflection X-ray fluorescence (TXRF) method for the determination of chlorine at trace levels in nuclear fuel samples is described. Chlorine present in trace concentrations in nuclear fuel materials such as U₃O₈, (U,Pu)C, PuO₂ and Pu-alloys was first separated from the solid matrix by pyrohydrolysis as HCl and was collected in 5mM NaOH solution. This solution was analyzed for chlorine by TXRF spectrometry using Cl Ka analytical line excited by W L_α. Cobalt was used as internal standard. The precision for such chlorine determination was found to be within 27% (n = 4) when the analysis was carried out in air atmosphere. This could be improved to 8% by making TXRF measurement in flowing helium atmosphere. The results obtained from TXRF determinations were also compared with those obtained from ion chromatography (IC) and were in good agreement. The collection of distillate during pyrohydrolysis in NaOH helped in counterchecking loss of chlorine during TXRF sample preparation. The average deviation of TXRF-determined values in helium-purged TXRF measurements with IC determined values (as chloride) was 15% at a chlorine concentration level in the range of 1–70μg/mL.