This research deals with a rectangular cavity encompassing two adiabatic rectangular and impermeable obstacles at various positions. This study serves as a platform to explore the interplay between diverse flow-governing parameters, such as the buoyancy ratio (N = −1, 0, and +1), Hartmann number (Ha = 0, 50, and 100), Lewis number (Le = 1, 5, and 10), Rayleigh number (Ra = 103 and 104), and geometric arrangements of twin-blocks (C1, C2, and C3) to help in developing insights into such complex transport phenomenon driven under the influence of buoyancy and concentration. The arrangements are chosen such that C1 and C3 represent the off-center position of the first obstacle, while C2 represents the in-line position with the second obstacle. The influence of liquid sodium–potassium alloy (Pr = 0.054) on fluid flow, heat, and mass transfer, and entropy generation characteristics due to double-diffusive natural convection in the twin obstacle-filled rectangular enclosure are observed using the lattice Boltzmann method. The results reveal that the maximum amount of heat and mass transfer occurs at the C2 position, making it the most efficient for heat and mass transfer among all. In contrast, the C2 configuration is a thermodynamically inefficient arrangement as entropy generation is maximum, while the C3 configuration is obtained to be more efficient thermodynamically. Furthermore, the results reveal that the average total entropy generation is directly related to the Lewis number, while it has an inverse relation with the Hartmann number.