Perhaps the greatest challenge in the graft copolymerization of acrylic acid onto starch initiated by Fenton’s is the selectivity of the grafting reaction. Low selectivity means that too much of unwanted homopolymer polyacrylic acid is produced. In this paper, it has been analyzed why with this reaction system, involving a water soluble monomer and indirect initiation, the graft selectivity is such a challenge. Several other grafting reactions, especially with monomers of low water solubility or when direct initiation is applied, show a better grafting performance. A scheme is presented based on reaction engineering principles, that supports an explanation of the observed differences. A more selective activation of starch is a factor, but perhaps even more important is a low monomer to starch ratio at the starting sites of graft reactions. Based on these insights, several methods to improve the graft selectivity are evaluated, with the help of literature data but mostly by experimental explorations in our laboratory. Most promising appears to be a dedicated dosage method, to add monomer in portions over time, tested in a batch reactor with gelatinized cassava starch. This way, both grafting percentage and graft selectivity could be improved. Such could not be realized with the more conventional dosage, which is to add all monomer before the start of the reaction. This can be considered a principal breaktrough. Still, more research and development would be needed to refine the method and to implement the idea also in a continuous reactor at larger scale.