The dehydration of bischofite is the key to the use of magnesium resource. Double salts or complex method is an important way to prepare anhydrous magnesium chloride. The crystals of bischofite and aniline hydrochloride were prepared through lowering the temperature of the mixture’s aquatic solution slowly. The pyrolysis of aniline hydrochloride, bischofite and the crystals was qualitatively analyzed by TG-FTIR under 400 ℃. We infered the reaction process through qualitative detection of escaping gas of each decomposition step. The Experimental results showed that there were three steps in the thermal decomposition of bischofite. In the first step, nearly four crystallized waters decomposed, while hydrolysis and decomposition took place together in the next two steps, but hydrolysis was the main reaction at the lower temperature (205～235 ℃), and comparative decomposition was the main one at the higher temperature (235～287 ℃). In the experimental temperature range, aniline hydrochloride didn’t decompose. Water and aniline hydrochloride left the crystals at different temperature, and no hydrolysis reaction occurred. Anhydrous magnesium chloride can be prepared though this way.