Type II carbon fibres (PAN-based) have been electrochemically oxidized in aqueous potassium nitrate to varying electron charge densities (0-4294 C g(-1)). The fibres were subsequently characterized by angle-resolved X-ray photoelectron spectroscopy (ARXPS) and ion scattering spectroscopy (ISS) and the results were correlated to acid/base surface titrations and BET surface area measurements. Relative to the as-received fibres (commercially treated, but unsized), the electrochemical treatments increased the ARXPS O/C atomic ratios by approximately 50%-100% and the concentration of oxidized carbon became more uniform within the XPS sampling depth (approximate to 10 nm). At the same time, the number of acidic functions titrated by sodium hydroxide rose from about 2.6 mu eq g(-1) to 1078 mu eq g(-1), and the BET surface area increased from 0.67 m(2) g(-1) to 2.9 m(2) g(-1). A large portion of the increase in acidic groups was due to the increased fibre oxidation below the XPS sampling depth. The surface densities of acidic functions (functions/nm(2)) determined from NaOH uptake and nitrogen BET surface area experiments were far larger than is physically possible. Thus, it is postulated that aqueous NaOH solutions are able to access a much larger surface region than can be measured by nitrogen BET. A model involving subsurface pores, voids, crevasses, etc., which become available via swelling during solvation in aqueous NaOH, but are at least partially closed off when dry (during BET measurements), was proposed. The quantity of acidic functions introduced (detected by NaOH) was directly proportional to the extent of oxidation as referenced to the electron charge density (C g(-1)). The ISS spectra suggest that the surface density of carbon/oxygen groups was also increased. Single-fibre fragmentation tests (using an epoxy resin matrix) revealed that in most cases the interfacial shear strengths (IFSS) increased with increasing ARXPS O/C atomic ratio probably due to enhanced fibre/matrix chemical bonding and/or mechanical interlocking. As the extent of the electrochemical oxidation progressed above 1500 C g(-1) the IFSS of single filament specimens then began to decrease. This was due to a continuing decrease in filament tensile strength as the extent of electro-oxidation increased. The critical transfer length, L-c, also decreased from similar to 0.36 mm to similar to 0.18 mm as the extent of electro-oxidation proceeded. Electrochemically oxidized fibres were compared to nitric acid-oxidized fibres in terms of acidic groups generated, BET surface areas, acidic group surface densities, dye adsorption with methylene blue and the role of aqueous NaOH in exposing some of the microstructure created by oxidative processes.