This work presents a comparative study of graphene exfoliation technologies from various graphite precursors—spectral graphite and thermally expanded graphite (Graflex)—using ultrasonic treatment and electrochemical methods in the presence of the ionic surfactant Nafion. The influence of exfoliation parameters, the nature of the starting material, and the presence of surfactant additives on the morphology, dispersibility, stability, and structural characteristics of the resulting graphene-containing dispersions was investigated. Particular attention is paid to a two-step technology combining pulsed electrochemical exfoliation with subsequent mild ultrasonic treatment. Comprehensive characterization of the samples was carried out using UV–Vis spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), electron microscopy, electron diffraction (ED), dynamic light scattering (DLS), and X-ray photoelectron spectroscopy (XPS). It was found that the use of Nafion significantly enhances exfoliation efficiency and contributes to the stabilization of the dispersions. Graphene sheets obtained from Graflex exhibit significantly larger lateral dimensions (up to 1 μm or more) compared to those exfoliated from spectral graphite (100–300 nm). The approach combining the use of Graflex and pulsed electrochemical exfoliation in the presence of Nafion with subsequent low-power ultrasonic treatment enables the production of few-layer graphene (1–3 layers) with high stability. © 2025 by the authors.