The aim of this work was to determine the limits of safe operation of continuous flow stirred‐tank reactor (CSTR) for the acid‐catalyzed hydrolysis of glycidol. The stability analysis was performed by dynamic modelling. The obtained results were compared with the experimental data reported in the open literature. For this purpose, dimensionless variables and parameters were introduced and unstable material and energy balances were defined. The system equations were solved using Matcont (Matlab ® software). Thus, bifurcation diagrams (in one and two dimensions) were mapped. All different dynamic states were identified and studied (thermal stability and instability, with unique and multiple solutions; Hopf bifurcations; turning points and envelope of periodic solutions). Finally, the intrinsic thermal unstable and cycle behavior of the acid‐catalyzed hydration of glycidol to produce glycerol was identified. The appropriate conditions to guarantee safe operation of CSTR were found. © 2016 American Institute of Chemical Engineers AIChE J , 62: 4418–4426, 2016