This work shows that thermoelectric (TE) topping generators can add 4-6% to the overall system efficiency for advanced supercritical steam turbines (Rankine cycle) that nominally generate power with 40-42% efficiency. The analysis then considers how this incremental topping energy can replace cooling water flow with air-cooled condensers (ACC) while maintaining current power output and plant efficiency levels with commensurate economic benefit ($/kW h). The simulated TE modules are located inside a coal-fired boiler wall constructed of wet steam tubes. The topping TE generator employs nontoxic and readily available materials with a realistic figure-of-merit range (ZT = 0.5-1.0). Detailed heat transfer and thermal analyses are included for this high-temperature TE application (e.g., 800 K for the cold side reservoir). With the tube surface enhanced by fins, the TE elements are designed to perform optimally through a distributed configuration along the wall-embedded steam tubes that are more than 20 m high. The distribution of the gas temperature in the furnace along the wall height is predicted by thermo-fluid dynamic analysis. This foundational design and analysis study produces overall realistic efficiency predictions in accordance with temperature-entropy analysis for superheated Rankine cycles. Lastly, the approach also allows for the addition of waste heat recovery from the flue gas. The analysis shows that the power output from the topping TE generator is significantly larger, compared to that from the waste heat recovery, due to the larger available temperature difference. (C) 2014 Elsevier Ltd. All rights reserved.