Export oil paintings, as a kind of early oil painting relics of China, not only depict the geographical landscapes and local customs of coastal cities in southern China, but also embody the techniques for making early local oil paintings in China. In this study, we used X-ray fluorescence spectrometry and scanning electron microscopy-energy spectrometry, in combination with Fourier transform infrared spectrometry and Raman spectrometry, to investigate the types and usages of white pigments used in Shanghai Bund, a 19th-century export oil painting from China. The results show that the white pigments used in the ground of this Qing Dynasty oil painting were mainly chalk (CaCO₃) and quartz (SiO₂), and that zinc carboxylate (metallic soap)—a reaction product of zinc-based pigments and oil media—was found in the paint layer. This study provides a reference basis for the research on materials and techniques and restoration and conservation of early export oil paintings from China.