Interfacial engineering plays a crucial role in regulating the quality and property of heterogeneous structures, especially for nanometerscaled devices. However, traditional methods for interfacial modulation (IFM) generally treat all the interfaces uniformly, neglecting the inherent disparities of interfaces like their growth sequence. Herein, it is found that the growthoriented characteristic of IFM strongly determines the main regions where the modulation takes effect. Specifically, in a semiconductor quantum well structure, the arsenic atoms modulated at the well-on-barrier (WoB) interface tend to diffuse into and thus affect the next-grown well layer. In contrast, the arsenic atoms introduced at the barrier-on-well (BoW) interface mainly take effect within the next-grown barrier layer. According to theoretical simulations and electron holography (EH) experiments, the depth of quantum wells and the height of potential barriers are extended by introducing arsenic atoms at WoB and BoW interfaces, respectively. Resultantly, while modulating at the BoW interface has little impact on the photoluminescence (PL) spectrum, applying IFM at the WoB interface could dramatically improve the luminescent intensity (about 30%), which demonstrates the impact of the growth-oriented characteristic. Furthermore, in situ bias EH results indicate that IFM at the WoB interface helps to suppress the quantum-confined Stark effect.