An optimization approach to enhancing the solar thermal decomposition of methane (TDM) reaction process based on the fluid flow pattern reconstruction is proposed. The sum of entropy generations due to TDM reaction and heat convection in the process is shown to tend to its maximum when the performance of the reaction is enhanced, and thus, is used as the criterial to optimize the velocity field of the fluid. This optimization problem is solved by the calculus of variations method. The obtained flow pattern is shown to be able to give the conditions to achieve the optimally enhanced TDM process. As the sum of the entropy generations tends to its extremum, the solution found by the optimization can be known as the thermodynamic limit for the TDM process enhancement. The obtained flow pattern can then be used to inspire the design of internal structures of the solar TDM reactor. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.