The transformation of alcohols to the corresponding alkyl chloride is one of the most important reactions in organic synthesis. This is because alcohols are one of the most common and versatile compounds for transformation to other classes of chemicals but they have the lower leaving ability. Most of the methods for the transformation utilize reagents such as thionyl chloride, phosphorus halides, hydrogen chloride gas, Vilsmeier-Haack, and Viehe salts. However, these traditional methods employed reagents above are invariably slow and conducted in harsh condition generally. Therefore, it is required to improve these drawbacks. We could meet these demands using green solvents in the presence of microwave irradiation. In contrast with the existing method under toxic organic solvents and traditional heating systems, we could reach at high yields for selective chlorination. General features of this synthetic method are Aluminum-catalyzed ( AlCl3.6H2O) selective chlorination of secondary alcohols, short reaction time due to MWI, no byproducts, and convenience of synthesis. It is expected that these advantages can allow our method to be used in a variety of synthesis.