The deconvolution theory of thermal transitions has proven to be a powerful method with which to analyze the heat capacity function of macromolecular systems. In this article, the basic results of the theory will be presented and their application to multistate transitions and general cooperative transitions of biopolymers and phospholipid membranes will be discussed. INTRODUCTION The development of highly precise differential scanning calorimeters has made possible the accurate definition of the heat capacity function associated with thermally-induced transitions of proteins, polypeptides, nucleic acids, lipid bilayers and other macromolecular systems. The importance of having experimental access to the exact shape of this function is that it contains all the information necessary to develop a complete thermodynamic description of a thermally-induced transition. In fact, it has been demonstrated that the excess heat capacity function can be appropriately transformed to yield the partition function of such a system and that this partition function can be used to deduce the microscopic mechanism of the transition (Refs. 1-6). In this article the analytical methods directed to obtaining a detailed statistical thermodynamic description of complex macromolecular systems will be presented. These methods constitute the basis of the deconvolution theory of thermal-transitions in macromolecules and, thus f.ar, have been applied to the study of protein unfolding reactions, helix-coil transitions in polynucleotides, thermal-transitions of transfer ribonucleic acids (tRNA) and biomembrane phase transitions. MACROMOLECULAR CONFORMATIONAL TRANSITIONS Most theories directed toward describing the molecular basis of function and modulation of biochemical systems include structural variations of the relevant macromolecules. Thus important questions relate to what are the characteristics of the equilibrium and dynamic fluctuations within an ensemble of such states. In general, the accessible structural states of a macromolecular system can be represented by the following reaction scheme: A+A A A (1) 0+ 1+ 2 n where the indexing of states is such that the enthalpy of state i (H.) is greater than the i-l state. (i.e. H>H.,). Thus as temperature i increased the population distribution mohotonically progresses toward state n. A normalized partition function for this system can be written in terms of the Gibbs energy differences as: