The invention discloses a device and a method for collecting toxic gas in high-temperature decomposition of materials. The device comprises a tubular cracking furnace and a sample boat, and further comprises a double-hole ball head inlet connector, a quartz combustion cylinder, a double-hole ball head outlet connector, an anti-inverse-suction buffer bottle, a gas absorption bottle, a drying tube,a dust filter, a needle valve, a flow meter and a gas storage bag, wherein the quartz combustion cylinder is located in the tubular cracking furnace. After being put into the sample boat, a sample ispushed to the high-temperature quartz combustion cylinder for combustion through a sample pushing magnetic block; after a part of the generated toxic gas is absorbed by an absorption liquid, the restof the toxic gas is dried and subjected to dust filtration; and the filtered toxic gas is collected in the gas storage bag. By the adoption of the device and the method, under the condition that gas flow of carrier gas is not interrupted, the sample can be rapidly and accurately fed; the test failure caused by the fact that a gas path is opened by impulsion at the moment of combustion can be avoided; the device is simple in structure, high in universality, short in analysis time, low in cost and convenient to operate; and the toxic gas can be better subjected to accurate qualitative and quantitative analysis.