Novel H-bond donor copolymers were designed by a versatile click type grafting reaction of unprotected mercaptoalcohols onto poly(2,3,4,5,6-pentafluorostyrene) (PPFS). As demonstrated by 19F NMR and Fourier transform infrared spectroscopy (FTIR) analyses, the reaction appears to be chemoselective as the SH groups solely react onto the para-fluoro position of the PFS units. The nucleophilic substitution was successfully performed with two mercaptoalcohols bearing either one or two hydroxyl groups. By carefully selecting the experimental conditions, a library of copolymers with various degree of substitution up to 95% was obtained in a reasonable timescale through kinetic control. By turbidity analysis, the ability of these functional polymers to form in solution interpolymer complexes with poly(4-vinyl pyridine) was shown to be tunable by adjusting the molecular characteristics. FTIR, X-ray photoelectron spectroscopy, and Differential scanning calorimetry evidence that different types of blends (immiscible, partially or totally miscible, and complex) can be achieved, and that the driving force of the interaction originates from H-bond.