Managing light-matter interactions on timescales faster than the loss of electronic coherence is key for achieving full quantum control of the final products in solid-solid transformations. In this Letter, we demon-strate coherent optical control of the orbital occupation that determines the insulator-to-metal transition in the prototypical Mott insulator V2O3. Selective excitation of a specific interband transition with two phase-locked light pulses manipulates the occupation of the correlated bands in a way that depends on the coherent evolution of the photoinduced superposition of states. A comparison between experimental results and numerical solutions of the optical Bloch equations provides an electronic coherence time on the order of 5 fs. Temperature-dependent experiments suggest that the electronic coherence time is enhanced in the vicinity of the insulator-to-metal transition critical temperature, thus highlighting the role of fluctuations in determining the electronic coherence. These results open different routes to selectively switch the functionalities of quantum materials and coherently control solid-solid electronic transformations.
