High second-order susceptibilities are created by thermal poling in bulk germanium disulfide based chalcogenide glasses. Experimental conditions of the poling treatment (temperature, voltage, time) were optimized for each glass composition. The second-order nonlinear signals were recorded by using the Maker fringes experiment and a second-order coefficient χ(2) up to 8 pm V–1 was measured in the Ge25Sb10S65 glass. This value is obtained using a simulation based on accurate knowledge of the thickness of the nonlinear layer. Two mechanisms are proposed to explain the creation of a nonlinear layer under the anode: the formation and the migration of charged defects towards the anode may mainly occur in Ge20Ga5Sb10S65 and Ge25Ga5S70 glasses, whereas the migration of Na+ ions towards the cathode may be responsible for the accumulation of negative charges under the anode in Ge33S67 and Ge25Sb10S65 glasses. Different electronic conductivity behaviors seem to be at the origin of the phenomenon. In parallel, the potential effect of the poling treatment on the structural and electronic properties is studied using Raman spectroscopy and secondary ion mass spectroscopy measurements.