Abstract: Accurate determination of zirconium (Zr) and hafnium (Hf) in zircon sands is essential for the evaluation and efficient utilization of mineral resources. Conventional wet chemical methods are often hampered by difficulties in sample dissolution, while X-ray fluorescence spectrometry (XRF) faces challenges such as a lack of high-concentration Zr-Hf reference materials, severe spectral line overlap and significant matrix effects. In this study, an XRF method based on pressed-pellet sample preparation was developed for the determination of Zr and Hf in marine placer samples. A broad-range, matrix-matched calibration series was constructed by blending zircon ore with national certified reference materials. To address spectral interference across different concentration ranges, dual calibration curves were established using the Hf Lα and Hf Lβ lines. Matrix effects and line overlap were effectively corrected using the Compton scattering internal standard method combined with empirical coefficient correction. Validation results showed relative errors below 10.2% and relative standard deviations (RSD) below 1.50% for both elements. The detection limits were 1.2 μg/g for Zr (Kα), 0.8 μg/g for Hf (Lα), and 7.0 μg/g for Hf (Lβ). The method was applied to marine placer samples collected from the eastern coastal area of Hainan, and the results were in good agreement with those obtained by inductively coupled plasma-mass spectrometry (ICP-MS) following the national standard method GB/T 20260-2006 (Part 10) with relative deviations of ≤6.2% for Zr and ≤10.6% for Hf. These findings demonstrate that the proposed method is suitable for high-throughput analysis and screening of marine placer resources.