The high-mobility conducting interface (CI) between LaAlO3 (LAO) and SrTiO3 (STO) has revealed many fascinating phenomena, including exotic magnetism and superconductivity. But, the formation mechanism of the CI has not been conclusively explained. Here, using in situ angle-resolved photoemission spectroscopy, we elucidated the mechanisms for the CI formation. In as-grown samples, we observed a built-in potential (Vbi) proportional to the polar LAO thickness starting from the first unit cell (UC) with CI formation appearing above 3 UCs. However, we found that the Vbi is removed by synchrotron ultraviolet (UV)-irradiation; The built-in potential is recovered by oxygen gas (O2(g))-exposure. Furthermore, after UV-irradiation, the CI appears even below 3UC of LAO. Our results demonstrate not only the Vbi-driven CI formation in as-grown LAO/STO, but also a new route to control of the interface state by UV lithographic patterning or other surface modification.