Application of clay minerals in bioremediation has emerged as a new and promising research field. In this study, the application of calcinated bentonite (CB) and calcinated organobentonite (COB) in phenanthrene (Phe) bioremediation showed high Phe removal efficiency. Clone libraries based on 16S rRNA gene and scanning electronic microscopy showed that diverse taxa of bacteria formed biofilms on both COB and CB particles. The family Sphingomonadaceae was the major group and made up 18% and 23% of the COB and CB biofilm composition, respectively. All and 80% of dioxygenase genes from COB and CB biofilms were closely related to that of Sphingomonas sp., and others matched to that of Comamonas and Mycobacterium. The selective effect of COB on bacterial community was also evident. This study characterized for the first time the bacterial diversity of biofilm community and functional Phe degrading groups on bentonites particles, and provided useful information for future applications. (C) 2013 Elsevier Ltd. All rights reserved.