We present a method for probing the quantum capacitance associated with the Rydberg transition of surface electrons on liquid helium using radio-frequency (RF) reflectometry. Resonant microwave excitation of the Rydberg transition induces a redistribution of image charges on capacitively coupled electrodes, giving rise to a quantum capacitance originating from adiabatic state transitions and the finite curvature of the energy bands. By applying frequency-modulated resonant microwaves to drive the Rydberg transition, we systematically measured a capacitance sensitivity of 0.34~aF/ for our RF reflectometry scheme. This sensitivity is sufficient to detect the Rydberg transition of a single electron, offering a scalable pathway toward qubit readout schemes based on surface electrons on helium.

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