Dendronized poly(diethylaminoethyl methacrylamide) (PEAM) was studied in blends containing isomeric cyclic dialcohols. Monomers and polymers were characterized by spectroscopic measurements. The phase behaviors of blends of PEAM with 1,2-, 1,3-and 1,4-cyclohexanediols (1,2-CHD, 1,3-CHD and 1,4-CHD, respectively) were established. Transparent films of the blends exhibited a single glass-transition temperature (T g ). Thermogravimetric analysis (TGA) revealed the temperature at which the polymer releases the small molecules. UV-vis spectra of 1,3-CHD and 1,4-CHD derivatives showed an isosbestic point that indicated the association of the alcohols. FT-IR measurements showed shifts in several absorption bands. The results were analyzed in terms of the side-chain structure and the interactions involved. AFM measurements revealed differences between the polymer and the blends. Compatibilization of blends of PEAM/CHDs occurred via the formation of hydrogen bonds, although hydrophobic interactions could not be disregarded.