Acting like thermal resistances, ferroelectric domain walls can be manipulated to realize dynamic modulation of thermal conductivity (k), which is essential for developing novel phononic circuits. Despite the interest, little attention has been paid to achieving room‐temperature thermal modulation in bulk materials due to challenges in obtaining a high thermal conductivity switching ratio (khigh/klow), particularly in commercially viable materials. Here, room‐temperature thermal modulation in 2.5 mm‐thick Pb(Mg1/3Nb2/3)O3–xPbTiO3 (PMN–xPT) single crystals is demonstrated. With the use of advanced poling conditions, assisted by the systematic study on composition and orientation dependence of PMN–xPT, a range of thermal conductivity switching ratios with a maximum of ≈1.27 is observed. Simultaneous measurements of piezoelectric coefficient (d33) to characterize the poling state, domain wall density using polarized light microscopy (PLM), and birefringence change using quantitative PLM reveal that compared to the unpoled state, the domain wall density at intermediate poling states (0< d33<d33,max) is lower due to the enlargement in domain size. At optimized poling conditions (d33,max), the domain sizes show increased inhomogeneity that leads to enhancement in the domain wall density. This work highlights the potential of commercially available PMN–xPT single crystals among other relaxor‐ferroelectrics for achieving temperature control in solid‐state devices. Thermal conductivity modulation in PMN–xPT single crystals is demonstrated with a maximum enhancement of more than 20% at the intermediate poling state (intermediate d33). The enhancement is attributed to the reduction in domain wall density due to alternating current poling. The thermal conductivity decreases at optimized poling (maximum d33) due to increasing domain size inhomogeneity.