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X-ray diffraction (XRD) is extensively used in archaeometric investigation. Herein, we provide a novel XRD spectrum-based untargeted strategy for the classification of ancient painted pottery for various dynasties. It was accomplished using the original spectrum without a phase identification. To eliminate the influence of baseline drift, a new baseline drift correction algorithm was specifically designed for XRD spectra. The algorithm was implemented using local minimum values in the analyzed signal in an iterative optimization manner. The results indicated that with the aid of the algorithm, the baseline drift problem can be successfully resolved, and the classification of ancient painted pottery can be greatly improved. Finally, the developed strategy was successfully used to discriminate ancient painted pottery from the Han and Tang dynasties in the cities of Guyuan and Zhongwei, China. The developed untargeted strategy had the remarkable advantage of almost automatic data analysis. The toolbox of our strategy can be obtained from the authors.