A novel, hydrophobically modified cationic polyacrylamide (HMPAM) was synthesized via the copolymerization of acrylamide, diallyl dimethyl ammonium chloride (DMDAAC), and diallylmethyl dehydroabietic acid propyl ester ammonium bromide. Optimum conditions for preparing HMPAM were such that the amount of initiator was 0.075 wt % of the total monomer mass, the monomer concentration was 20 wt %, and the amount of DMDAAC was 18 mol % of the total monomer molar mass. HMPAM was characterized with an UV–visible spectrometer, 1H‐NMR, Ubbelohde viscometer, rotational viscometer, and rotational rheometer. HMPAM solutions exhibited strong hydrophobic associations, and the critical association concentration of the HMPAM aqueous solution was about 0.7 wt %; the HMPAM solutions also showed salt thickening and shear resistance. The surface morphologies of the freeze‐dried HMPAM samples (1 wt %) were also observed via scanning electron microscopy. Compared with unmodified cationic polyacrylamide, Synthesis of HMPAM‐0.5 exhibited a stronger flocculation capacity, and the optimal transmittance of the supernatants was above 95%. HMPAM‐0.5 showed significant flocculation performances for 3–4 and 3–5 wt % kaolin suspensions at 40 and 50 mg/L, respectively. Moreover, the flocculation performance was enhanced with the addition of NaCl and CaCl2. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46637.