The use of isothermal microcalorimetry for analyzing structural relaxation and recovery processes of amorphous materials is discussed. Unlike the conventional DSC method, this new method enables to directly monitor the relaxation process. Also featured in this article is its application for investigating the recovery process, which has hardly been reported in literature. The both processes were elucidated using Kohlrausch-Williams-Watts derivative, although its application for the recovery process needs discussion. The relaxation parameters obtained by this procedure agreed very well with those from the DSC method. The advantages and disadvantages of this method are summarized.