Paramylon is a natural hydrophilic polysaccharide produced in the pyrenoids of euglenoids, and esterification may render paramylon hydrophobic. Esterification imparts not only thermoplasticity, but also potential compatibilities with other polymer resins and fillers. However, the dependence of the compatibility on the structure of the polymer ester has not yet been systematically studied. To estimate the affinities between paramylon esters and hydrophobic organic solvents/resins, the dependences of their Hansen solubility parameters, which are association indices, on the degrees of substitution and chain lengths of the ester groups were investigated. Experimental and theoretical investigations were conducted using the dissolution and Fedors methods, respectively. Esterification decreased the solubility parameter from 49 (paramylon) to approximately 18 MPa1/2 (paramylon esters), indicating that the potential affinities of paramylon esters for hydrophobic organic solvents/polymers increased. A multiple regression analysis was also performed to investigate the effects of acyl chain length and degree of substitution with acyl groups on the solubility parameter. The solubility parameters of the paramylon derivatives were continuously variable from hydrophilic to ‐phobic. Hence, esterification with various acyl groups may control the hydrophobicities of paramylon esters, enhancing their miscibilities with various hydrophobic organic solvents and resins.