Abstract: A synthesis protocol was identified to produce covalent grafting of poly(dimethyl siloxane) from cellulose, based on prior studies of analogous ring opening polymerizations. Following this polymer modification of cellulose, the contact adhesion was anticipated to be modified and varied as a function of the polymer molecular mass. The synthetic details were optimized for a filter paper surface before grafting the polymer from bulk cellulose spheres. The adhesion of the unmodified and grafted, bulk cellulose spheres were evaluated using the Johnson–Kendall–Roberts (JKR) theory with a custom build contact adhesion testing setup. We report the first example of grafting poly(dimethyl siloxane) directly from bulk cellulose using ring opening polymerization. For short grafting lengths, both the JKR work of adhesion and the adhesion energy at the critical energy release rate (Gc) were comparable to unmodified cellulose beads. When polymer grafting lengths were extended sufficiently where chain entanglements occur, both the JKR work of adhesion and Gc were increased by as much as 190%. Given the multitude of options available to graft polymers from cellulose, this study shows the potential to use this type of cellulose spheres to study the interaction between different polymer surfaces in a controlled manner. Graphical abstract: [Figure not available: see fulltext.].