A sub-micrometer size beam (0.5μm diameter) in a position-resolved small angle X-ray scattering set-up (μSAXS) has been used for the characterization of chemically activated carbon fibers (ACF). These materials have been prepared from isotropic carbon fibers (pitch carbon fibers) and anisotropic carbon fibers (PAN-based carbon fibers) by chemical activation with KOH and NaOH. The μSAXS experimental set-up made it possible to analyze different regions of a single fiber across its diameter and to distinguish the structural features already existing in the raw fibers or being created during the activation process. The results showed that depending on the precursor, the chemical activation process produces isotropic or anisotropic development of porosity. It was observed that chemically ACF prepared from isotropic carbon fibers present an isotropic development of the porosity and that a high micropore volume is developed not only in the external region of the fiber, but also in the core. On the other hand, in the case of anisotropic PAN-based carbon fibers the existence of two regions with different structure was detected by μSAXS measurements across the fiber diameter: an anisotropic external ring and a more isotropic fiber core. The results showed that these two regions remain after chemical activation and that the activating agents are reaching the fiber core. It seems that the more isotropic fiber core is activated easier by NaOH than KOH.