Polyethylene (PE) and polystyrene (PS) are commercial plastics with large amounts of output, and their wastes have brought serious burden to our living environment. These usually exist as PE/PS mixtures and are hard or expensive to sort in some cases. PE/PS blends have poor mechanical properties due to thermodynamic incompatibilization. In principle, ethylene/(phenyl functionalized alpha-olefin) copolymers (containing PE and continuous phenyl alpha-olefin segments on one polymeric chain) would be good compatibilizers for PE/PS, but the synthesis of corresponding copolymers is much more difficult. Herein, we report the synthesis of ethylene-styrene (E-St), ethylene-allylbenzene (E-AP), and ethylene-(4-phenyl-1-butene) (E-BP) copolymers containing continuous comonomer segments via the copolymerization of E with various phenyl functionalized alpha-olefin monomers (St, AP, and BP) catalyzed by thiophene-fused cyclopentadienyl scandium complexes and study the compatibilization of resultant copolymers for HDPE/PS blends by using tensile test experiment and SEM and TEM analyses. E-BP copolymers behaved like adhesive materials with high BP incorporation ranged from 13.5 to 24.1 mol % and showed better compatibilization effect for HDPE/PS blends compared with E-St and E-AP, probably because of the longer distance between the polymeric main chain and phenyl group on its molecular structure, which favors the intermolecular pi-pi interaction between E-BP and PS during melting mixing. HDPE/PS/P4 (weight ratio: 80/20/2) blend (P4: E-BP copolymer with 24.1 mol % BP content) exhibited the greatest improvement in elongation at break (1397%), which showed a 26.3% increase, compared with the uncompatibilized HDPE/PS (80/20) blend and reached 91.5% of ultimate elongation of pure HDPE, and its tensile stress was also close to that of HDPE, indicating that P4 could be used as an effective compatibilizer for HDPE/PS mixtures that are difficult or expensive to sort.