The discovery of filling-controlled phase modulations in correlated systems opens an emerging paradigm to unlock unique electromagnetic states and physical phenomena, transcending traditional paradigms. Here, correlated $\mathrm{V}{\mathrm{O}}_2$ (B) is selected as a model system to realize multiple electronic phase modulations through ionic evolution, leveraging the inherent ${\mathrm{V}}_4{\mathrm{O}}_{10}$-type double-layered structure and thermodynamic metastability. The introduction of electron carriers into the $\mathrm{V}-3d$ orbital of metastable $\mathrm{V}{\mathrm{O}}_2$ (B), as driven by ${\mathrm{W}}^{6+}$ substitution, oxygen deficiency, or protonation, triggers the carrier delocalization, giving rise to sequential electronic phase modulations, beyond well-established M1 and R phases of $\mathrm{V}{\mathrm{O}}_2$. Of particular note is the synergistic interplay between oxygen defects and interstitial protons in cooperatively driving electronic state evolutions in $\mathrm{V}{\mathrm{O}}_2$ (B) through band-filling regulation, enabling the robust control over the energy landscape in a reversible pathway. Utilizing synchrotron-related spectroscopy techniques and theoretical calculations, we reveal that the band filling in low-energy ${\pi }^{*}$ orbital of $\mathrm{V}{\mathrm{O}}_2$ (B) through electron doping governs electronic phase modulations, delivering a unified physical picture. Our findings not only demonstrate a powerful tuning knob for adjusting correlated electronic states in metastable layered-structure materials, fostering exotic physical functionalities and phenomena but also extend the horizons in materials designs for iontronic device applications.

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• Critical phenomena
• Phase transitions
• Semiconductors
• Thin films