Traditional fossil fuel power generation process typically has low efficiency. Large amount of the energy loss in Rankine cycle steam turbines (ST) is due to the temperature difference between the combustion flame temperature ∼2250 K (adiabatic) and the high pressure steam temperature up to 900 K. However, some of this energy can be harvested using solid-state thermoelectric (TE) power generators which are placed into the gap between the flame temperature and the steam temperature that produce additional electrical power. This study investigates the potential placement of TE on water tube wall inside a boiler at a coal-fired power plant. Three-dimensional (3D) numerical model of a simplified TE module is developed, and hot gas temperature and steam temperature from the boiler are used as boundary conditions at the hot side and cold side of the TE. The numerical results are compared with analytical calculations. The 3D effects of the thermal spreading in the TE module are investigated. Parameters such as TE leg cross section area and TE fill factor are examined in order to maximize the electrical power production of the TE without sacrificing the boiler efficiency (i.e., reducing the steam temperature). The study also looks into the various locations inside the boiler that have good potential for TE installation.