Cooperative relaxation of glycerol and its four aqueous solutions (60%, 70%, 80% and 90% by mass) has been investigated in terms of the nonlinear Adam-Gibbs (AG) enthalpy relaxation theory using differential scanning calorimetry (DSC). The AG parameters were obtained using curve-fitting method. The results indicated that the relaxation time of glycerol/water mixtures is water- sensitive. With the changing of water content, regular trend was found in both the equilibrium and the glassy state. The fitting results were used to estimate the microscopic parameters of the cooperative rearranging region (CRR), in particular the size of the CRR (z*) and the configurational state available to it (W*). The results showed that the W* recommended for polymers led to physically meaningless z* for glycerol and its aqueous solutions. Johari's method, which still based on the AG theory, yielded three to four molecules in the CRR. But the W* is anomalistically higher than those of polymers. With the changing of the water content, the size of CRR estimated using Donth formula seemed to be reasonable according to the analysis of the apparent activation energy (Delta h*), the distribution parameter the of relaxation times (P). But it is difficult to reconcile the Adam-Gibbs' z* with the results obtained using Donth's formula. (c) 2007 Elsevier B.V. All rights reserved.