Precise control of the hetero-epitaxy on a low-cost foreign substrate is often the key to drive the success of fabricating semiconductor devices in scale when a large low-cost native substrate is not available. Here, we successfully synthesized three different phases of Ga2O3 (α, β, and ε) films on c-plane sapphire by only tuning the flow rate of HCl along with other precursors in an MOCVD reactor. A threefold increase in the growth rate of pure β-Ga2O3 was achieved by introducing only 5 sccm of HCl flow. With continuously increased HCl flow, a mixture of βand ε-Ga2O3 was observed, until the Ga2O3 film transformed completely to a pure ε-Ga2O3 with a smooth surface and the highest growth rate (~1 µm/hour) at a flow rate of 30 sccm. At 60 sccm, we found that the film tended to have a mixture of αand ε-Ga2O3 with a dominant α-Ga2O3, while the growth rate dropped significantly (~0.4 µm/hour). The film became rough as a result of the mixture phases since the growth rate of ε-Ga2O3 is much higher than α-Ga2O3. In this HClenhanced MOCVD mode, the Cl impurity concentration was almost identical among the investigated samples. Based on our density functional theory calculation, we found that the relative energy between β-, ε-, and α-Ga2O3 became smaller thus inducing the phase change by increasing the HCl flow in the reactor. Thus, it is plausible that the HCl acted as a catalyst during 2 the phase transformation process. Furthermore, we revealed the microstructure and the epitaxial relationship between Ga2O3 with different phases and the c-plane sapphire substrates. Our HClenhanced MOCVD approach paves the way to achieving highly controllable hetero-epitaxy of Ga2O3 films with different phases for device applications.