As a kind of special paper artifact, memorials are considered physical evidence that embody the emperor’s culture, of which the paper-making and dyeing process reflect the political culture and social development level of the Qing Dynasty. The composing materials of the memorial are fragile. Previous research on memorials have mainly focused on text content, style, political influence and restoration, while the analysis towards the original materials and crafts is relatively scarce. By employing various in situ non-destructive techniques, a systematical study has been conducted on the paper-making and dyeing process of a memorial from Cen Chunxuan, an important minister in the late Qing Dynasty. UV fluorescence photography and FTIR spectra showed that the yellow damask-decorated patterns on the folding page and envelope were woven with silk products. Comprehensive analysis results of ultra-depth-of-field microscopic observation, Raman spectroscopy and XRF demonstrated that the mineral pigment Orpiment with a pretty fine graininess was used to dye the memorial paper through the brush dyeing method. Orpiment is more expensive than organic dyes such as Phellodendron amurense, which not only raises the ability of moth and water resistance but also highlights the significance of memorials in the Qing Dynasty’s institutional culture. It is another discovery in the case of paper dyeing yellowing. In addition, this article also explored the application of optical fiber fluorescence spectroscopy to analyze the pigment of comments written in red on the memorial and found that the red handwriting was written in cinnabar, which was consistent with the results of Raman spectroscopy and XRF. The investigation of the materials and crafts of such paper artifacts as memorials promotes the understanding of the technical characteristics of the paper-making and dyeing process in the Qing Dynasty. It provides the scientific basis for the rational protection and restoration of such cultural relics. At the same time, this article also discussed the applicability of fiber optic fluorescence spectroscopy in identifying pigments used in paper artifacts, which further expanded the types and applications of non-destructive analysis techniques.