Complementary techniques, including low-temperature nitrogen adsorption and small-angle X-ray scattering (SAXS), are applied to detect the effects of surface functionalization on the morphology of activated carbon derived from poly(ethylene terephthalate) (PET). Scanning electron microscopy (SEM) is also employed as an auxiliary method to visualize the surface below the micron scale. The SEM images reveal a micron-sized ridgelike texture. Room temperature acid treatment makes the ridges become more pronounced, while treatment with boiling acid uncovers fiberlike structures of roughly 1 microm diameter. All samples display an apparent surface fractal dimension of Ds = 2.4 in the wave vector range 0.001-0.02 A(-1). Nitric acid at room temperature increases the surface oxygen content only by 3 at. %, while all the adsorption properties and structural parameters reported in this paper are virtually unaffected. Significant differences in the morphology at submicron scales appear only after boiling acid treatment. The resulting carbon remains highly microporous, but the loss of Brunauer-Emmett-Teller (BET) surface area from about 1150 to 304 m2/g is approximately 75%. In addition to the principal peak at around 8 A, fresh peaks appear in the polydisperse Horvath-Kawazoe (HK) pore size distribution owing to the burnoff of intervening walls. The average width of the slitlike pores calculated from the Dubinin-Radushkevich (DR) plot increases from 8.4 to 11 A. The minimum slit width where the applied probe molecules, that is, nitrogen and hexane, can enter increases from about 5 to about 5.4 A. The separation distance of the basic structural units is practically unchanged. When, however, this carbon is in contact with hexane, this distance expands from about 19 to 27 A. The swelling is consistent with the deformable nature of this sample also illustrated by the low-pressure hysteresis and the reduced helium density. Particular attention was paid to the surface areas derived from low-temperature nitrogen adsorption and X-ray measurements. Owing to the wide spatial range of the structures in these samples, estimates of the specific surface area of activated carbons can be substantially in error unless both upper and lower q ranges of the SAXS spectra are taken into account. Surface areas derived from the adsorption data either by the BET or the DR approaches were always below the values obtained by standard SAXS. As an example, the carbon sample functionalized at room temperature gave surface area values of 1114, 1293, and 1970 m2/g, respectively. The possibility that this difference is caused by inaccessible pores was excluded by contrast variation measurements with hexane.