The interfacial structural coupling, electronic transfer, and particle coupling behaviors in heterojunctions composed of transition metal oxides (TMOs) and transition metal dichalcogenides (TMDCs) can profoundly affect the original lattice structures, charge dynamics, and spin degrees of freedom, potentially leading to novel physicochemical phenomena and the elucidation of new physical mechanisms. However, the control of interface quality in such systems is often neglected, which can compromise the functionality of these heterojunctions. There is a notable paucity of direct research evidence regarding how the surface structure control of TMO single crystals influences the synthesis and properties of TMDCs. In this study, we have selected Al 2 O 3 (0001), TiO 2 (110), and SrTiO 3 (111) as representative TMO substrates. Through precise etching and annealing treatments, we achieved atomically flat stepped surfaces on these substrates. Subsequently, we investigated the impact of these ordered atomic steps on the chemical vapor deposition (CVD) growth of MoS 2 , comparing them with the disordered surfaces of untreated single crystals. Furthermore, we utilized the polarized negative excitons in the SrTiO 3 /MoS 2 composite system as a probe to explore the extent of polarization coupling under varying interfacial conditions. This research aims to underscore the critical importance of interfacial orderliness of oxide single crystal surfaces in modulating the growth of TMDCs and their interactions with TMOs. By highlighting the significance of interface orderliness, we seek to advance the understanding of effective interfacial interactions in these composite systems.