Using ammonia as working fluid, enthalpy equations corresponding to every point in Rankine cycle for low-grade thermal energy conversion (LTEC) are presented by employing curve-fitting method. Analytical equations of Rankine cycle analysis are thus set up. In terms of temperatures of the evaporator and condenser, the equation related to Rankine cycle net power output is then achieved. Furthermore, by using theoretical optimization method, the results of the maximum net power output of a Rankine cycle in LTEC are also reported. This study extends the recent flurry of publications about Rankine cycle power optimization in LTEC, which modified the ideal Rankine cycle to a Carnot cycle by using an average entropic temperature to achieve the theoretical formulas. The proposed method can better reflect the performance of Rankine cycle in LTEC since the current work is mainly based on the direct simulations of every enthalpy points in Rankine cycle. Moreover, the proposed method in this paper is equally applicable for other working mediums, such as water and R134a.