摘要： This paper reports the dry and wet synthetic procedures and characterization by Raman spectroscopy of amorphous arsenic sulfide reference pigments. Reference spectra of two amorphous materials obtained by wet process methods and four dry process references of amorphous arsenic sulfide pigments of known composition are presented and discussed. While all materials present a main band characteristic for the amorphous pigment centered on 341 cm?1, additional small contributions indicate the presence of sulfur, arsenic oxide, and crystalline nano phases embedded in the amorphous matrix. Although only the broad 341‐cm?1 peak is necessary to identify the arsenic sulfide as an amorphous material, the smaller additional features allow for the characterization of the various manufacturing processes and initial materials used. In ideal conditions, these small features also enable to assess the As/S ratio of the studied amorphous arsenic sulfide pigments based on their relative intensity. In this context, the latter reference spectra were used to characterize the amorphous arsenic sulfide pigments and their arsenic to sulfur elemental composition in four 18th‐ to 20th‐century historical samples and compared with scanning electron microscopy with energy dispersive X‐ray semiquantitative analyses. The identification of the amorphous arsenic sulfide used in these historical samples was compared with the description of the manufacturing processes reported in historical sources of the time, allowing for a better understanding of the evolution of the amorphous arsenic sulfide pigments manufacturing methods.