Chemical modification of wood cellulose fibers is important for tailored wood–polymer interfaces, reduced moisture sorption, and novel grades of chemical wood pulp. The present study shows how the reaction solvent system influences hydroxyl accessibility during chemical fiber modification. Surface initiated ring-opening polymerization of ε-caprolactone from wood cellulose fibers was investigated in a wide range of solvent systems. The hydrogen bond donor strength of the solvent increased graft density and the amount of grafted polycaprolactone (PCL) on the fiber surface, and on nanoscale fibrils inside the fiber. Specifically, the reaction system with acetic acid as a new, green solvent for cellulose grafting increased graft density 24 times compared to bulk polymerization conditions. The results show relationships between solvent properties, hydroxyl accessibility, and grafting results in cellulosic plant fibers. The study clarifies the opportunities provided by controlling the interior of the cellulosic plant fiber cell wall during chemical modification so that the fiber becomes a swollen cellulose nanofibril gel.