Alkali metal dosing has nowadays been extensively used in angle-resolved photoemission spectroscopy (ARPES) for the in situ surface electron doping of materials to provide access to the unoccupied states. This technique also gives rise to nontrivial physical phenomena, such as the appearance of quantum well states and effects due to alkali metal intercalation. Here, we uncovered a previously unobserved type of electronic behavior induced by alkali metal dosing. By employing ARPES to study the evolution of the electronic structure of the Ti2O3 thin film upon rubidium (Rb) dosing, we found that the electron chemical potential of the system remains unchanged throughout the process. Interestingly, a series of electron-like band dispersions first appear with Rb dosing. A further increase in the Rb dosage leads to the eventual disappearance of the electron-like bands and the emergence of a set of hole-like bands. Our finding enriches the phenomenology brought about by alkali metal surface dosing, suggesting a novel functionality of this popular surface doping technique.