X-ray photoelectron spectroscopic (XPS) data have been recorded for a low-molecular-weight poly(ethylene glycol) microliter-sized sessile liquid drops sitting on a dielectric covered planar electrode while imposing a +/- 6 V square-wave actuation with varying frequencies between 10(-1) and 10(5) Hz to tap into the information derivable from (AC) electrowetting. We show that this time-varying XPS spectra reveal two distinct behaviors of the device under investigation, below and above a critical frequency, measured as similar to 70 Hz for the liquid poly(ethylene glycol) with a 600 Da molecular weight. Below the critical frequency, the liquid complies faithfully to the applied bias, as determined by the constant shift in the binding energy position of the XPS peaks representative of the liquid throughout its entire surface. The liquid completely screens the applied electrical field and the entire potential drop takes place at the liquid/dielectric interface. However, for frequencies above the critical value, the resistive component of the system dominates, resulting in the formation of equipotential surface contours, which are derived from the differences in the positions of the twinned O 1s peaks under AC application. This critical frequency is independent of the size of the liquid drop, and the amplitude of the excitation, but increases when ionic moieties are introduced. The XP spectra under AC actuation is also faithfully simulated using an equivalent circuit model consisting of only resistors and capacitors and using an electrical circuit simulation software. Moreover, a mimicking device is fabricated and its XP spectra are recorded using the Sn 3d peaks of the solder joints at different points on the circuit to confirm the reliability of the measured and simulated AC behaviors of the liquid. These new findings indicate that in contrast to direct current case, XPS measurements under variable frequency AC actuation reveal (through differences in the frequency response) information related to the chemical makeup of the liquid(s) and brings the laboratory-based XPS as a powerful complimentary arsenal to electrochemical analyses of liquids and their interfaces.