Micro-electrodes were applied to anaerobic granular sludge, which was developed in a UASB reactor, to examine intra-granule profiles with respect to pH, glucose and sulfide. When glucose was employed as a bulk liquid substrate, the micro-electrodes study demonstrated the pH behavior along granule depth: pH decrement at the granule exterior portion due to acid formation (buildup of acidity), and subsequent pH increment at the granule inner portion due to the consumption of acid (buildup of alkalinity). Sulfide micro-electrode proved sulfate reduction that mostly occurred at the granule exterior portion. Chemical equilibrium consideration evidently explained the occurrence of ferric sulfide predominantly in the interior portion, which accounts well for the morphology of a representative double-layered structure of granules grown on a low level of sulfite. Inorganic elements distribution within anaerobic granule was examined by electron probe X-ray micro analysis (EPMA) and ICP methods. The presence of crystalline calcium carbonate (calcite) was identified by X-ray diffraction analysis.