Energy dispersive X-ray fluorescence studies on determination of thorium (in the range of 7 to 137 mg/mL) in phosphoric acid solutions obtained by dissolution of thoria in autoclave were made. Fixed amounts of Y internal standard solutions, after dilution with equal amount of phosphoric acid, were added to the calibration as well as sample solutions. Solution aliquots of approximately 2–5 μL were deposited on thick absorbent sheets to absorb the solutions and the sheets were presented for energy dispersive X-ray fluorescence measurements. A calibration plot was made between intensity ratios (Th Lα/Y Kα) against respective amounts of thorium in the calibration solutions. Thorium amounts in phosphoric acid samples were determined using their energy dispersive X-ray fluorescence spectra and the above calibration plot. The energy dispersive X-ray fluorescence results, thus obtained, were compared with the corresponding gamma ray spectrometry results and were found to be within average deviation of 2.6% from the respective gamma ray spectrometry values. The average precision obtained in energy dispersive X-ray fluorescence determinations was found to be 4% (1σ). The energy dispersive X-ray fluorescence method has an advantage over gamma ray spectrometry for thorium determination as the amount of sample required and measurement time is far less compared to that required in gamma ray spectrometry.