In this paper, the morphological transformations in $Hibiscus$ $sabdariffa$ stem fiber on graft copolymerization with acrylonitrile (AN) and its binary mixture with methyl acrylate (MA) and acrylamide (Aam), using ceric ammonium nitrate - nitric acid initiator system has been reported. Different reaction parameters such as temperature, time, initiator concentration, monomer concentration and pH were optimized to get the maximum graft yield (Pg:28.0) and used in binary monomeric mixture to further improve the properties. The graft copolymer thus formed were characterized by FTIR, SEM, XRD, TGA, and DTA techniques. The percentage crystallinity and crystallinity index were found to decrease with increase in percentage grafting. The graft copolymer were found to be moisture, chemical and thermal resistant for various advanced applications.