Non-destructive measurement methods including video microscopy (VM), Raman spectrometer (RS), and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) were employed to analyze the printing materials of a green curled-up dragon stamp sample from the late Qing Dynasty in terms of the paper and ink. The results indicated that the plate-making process of the sample belonged to handcrafted gravure while the slender and dense paper fiber with no coating, watermark, or gumming. Elements of Al and Si were inspected in fillers of paper, therefore, it could be inferred that kaolin (Al2O3·2SiO2·2H2O) was the filler of paper. Green ink was made up of blue pigment Prussian Blue (Fe4［Fe(CN)6］3·14-16H2O) and yellow pigment Lead(II) chromate(PbCrO4). According to theories of additive color and subtractive color, ink presented green color due to the effect of Prussian blue and Lead chromate mixed together. Elements of Na, Mg, S, Cl, K, Ca, V, Zn and Ba were measured from fillers of the ink and it could be inferred that MgCO3, BaSO4, CaCO3 and other substances might be contained in ink fillers. This study with three techniques mentioned above is viable and it has a broad application in non-destructive analysis of printing and paper-based artwork.