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Electronic states and their dynamics are of critical importance for electronic and optoelectronic applications. Here, various relevant electronic states in monolayer MoS2, such as multiple excitonic Rydberg states and free‐particle energy bands are probed with a high relative contrast of up to ≥200 via broadband (from ≈1.79 to 3.10 eV) static third‐harmonic spectroscopy (THS), which is further supported...