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Actually, it does work.  People have used it for controlling moisture in basements for many years. The chemistry is fairly simple.  The water molecule is attracted to the Calcium ion in a somewhat exothermic process using what is known as heat of enthalpy.  Google calcium chloride moisture...

CaCl2, calcium chloride can be very helpful in controlling excess moisture.  It is cheap, environmentally gentle, readily available at Walmart, Home Depot, and even $ stores.  Look for brand names like Damp rid.  CaCl2 pellets are also used to melt snow and ice.  People have been using it to...