The structures of pseudo-binary GeS2-Sb2S3, GeS2-CdS, Sb2S3-CdS, and pseudo-ternary GeS2-Sb2S3-CdS chalcogenide systems are systematically investigated by Raman spectroscopy. It is shown that a small number of [S3Ge-GeS3] structural units (SUs) and -S-S-/S-8 groups exist simultaneously in GeS2 glass which has a three-dimensional continuous network backbone consisting of cross-linked corner-sharing and edge-sharing [GeS4] tetrahedra. When Sb2S3 is added into GeS2 glass, the network backbone becomes interconnected [GeS4] tetrahedra and [SbS3] pyramids. Moreover, Ge atoms in [S3Ge-GeS3] SUs tend to capture S atoms from Sb2S3, leading to the formation of [S2Sb-SbS2] SUs. When CdS is added into GeS2 glass, [Cd4GeS6] polyhedra are formed, resulting in a strong crystallization tendency. In addition, Ge atoms in [S3Ge-GeS3] SUs tend to capture S atoms from CdS, resulting in the dissolution of Ge-Ge bond. Co-melting of Sb2S3 or CdS with GeS2 reduces the viscosity of the melt and improves the homogeneity of the glass. The GeS2 glass can only dissolve up to 10-mol% CdS without crystallization. In comparison, GeS2-Sb2S3 glasses can dissolve up to 20-mol% CdS, implying that Sb2S3 could delay the construction of [Cd4GeS6] polyhedron and increase the dissolving amount of CdS in the glass.