The relevance of polarity and solubility of vinyl monomers in graft polymerization onto starch was re-examined employing a wide spectrum of vinyl monomers. In the light of earlier assumptions that higher the polarity and solubility of the vinyl monomer, higher will be the grafting, the present investigation, in stark contrast, has brought forward the fact that the graft polymerization is independent of the polarity and solubility of the vinyl monomer. And that no interrelation, whatsoever, exists between the grafting ability of a vinyl monomer and its polarity and solubility. Ceric ammonium nitrate was used as the graft initiator. Percentage grafting, grafting efficiency and homopolymer contents were the parameters that were used for monitoring the graft polymerizations. Infrared and acid hydrolysis techniques were used for the confirmation of graft copolymer formation. Interestingly, in the case of n-alkyl acrylates and methacrylates, as the length of the n-alkyl group increases, the grafting percentage and homopolymer content decrease which was attributed to their increase in steric hindrance. As a minor part, an overall review of the various monomers for their ability to graft polymerize and homopolymerize was done.