Fly ash collected from a local captive power plant has been fully characterized in respect of its physico-chemical, morphological, and mineralogical features. The high carbon ash consists of large unburnt, irregular carbonaceous particles, which appear to be porous. The non-magnetic particles are more irregular in shape as compared to their magnetic counterpart. Fe bearing crystallites appear in a variety of geometrical patterns on the surfaces of magnetic components. Some of the coarser fractions of the ash have high calorific value and may be used as domestic fuel. The causes for inefficient combustion of the feed coal used have been identified and possible remedies suggested. The presently reported work is expected to be a good beginning for proper management of high carbon ash-generated by several captive power plants in India.