This paper deals first with the flotability characteristics of petrographic constituents in Shenfu coals, Some differences, such as elemental composition, ash level, oxygen-containing functional groups, hydrophilicity and zeta-potential, between vitrain (vitrinite-rich lithotype) and fusain (inertinite-rich lithotype) were established. These differences give rise to the possibility of separating and preparing single constituents by means of the flotation method. Tests verified that when appropriate reagents, such as frothers, collectors, etc., are used during flotation, it is possible to separate vitrinite from coals. The results showed that vitrinite in the floats can reach more than 80% if accumulative yields of flotation for sludge are maintained in some degree, such as below 69%.