The simulated annealing algorithm is introduced to search the global optimal solutions for the multipeak phenomena which generally exist in the phase stability problems with continuous variables. The Gibbs free energy criterion was modeled by the NRTL and UNIQUAC activity coefficient equations. When previous approaches fail, it is usually because they locate local minima due to the nonconvex and nonlinear natures of the models used to predict phase equilibrium. In this paper, the preliminary results show that the global minimum of the tangent plane distance function (TPDF) can be obtained by using the simulated annealing algorithm. The effects of the initial and the final values of the control parameter, the decrement of the control parameter and the length of the Markov chains are analyzed. The optimal ＇cooling schedule＇ was obtained according to the calculation results of the phase stability problems for one ternary mixture. The liquid-liquid equilibrium compositions were calculated by the Newton-Raphson method on the basis of the global minimum of TPDF. The results of four examples show that the simulated annealing algorithm can effectively solve the global phase stability problem.