The　non-polar　characteristics　of　polyolefins　limit　their　applications.　Introducing　polar　functional　groups　to　polyolefins　can　greatly　improve　their　properties　and　further　expand　their　application　range.　Here,　a　Barbier　polymerization　method　is　demonstrated　to　be　a　versatile　strategy　to　synthesize　polar　polyolefin　analogues　(PPAs),　which　are　further　utilized　as　modifiers　to　improve　the　properties　of　non-polar　polyolefins　by　physically　introducing　polar　functional　groups.　Through　this　Barbier　polymerization　method,　a　series　of　novel　hydroxyl　group-containing　PPAs　are　synthesized.　The　successful　preparations　of　PPAs　are　characterized　by　nuclear　magnetic　resonance,　gel　permeation　chromatography　and　Fourier　transform　infrared　spectroscopy.　PPAs　are　further　applied　as　modifiers　of　linear　low-density　polyethylene　(LLDPE).　Characterization　studies　including　scanning　electron　microscopy,　differential　scanning　calorimetry,　contact　angle　measurements,　rheological　testing,　and　tensile　testing　reveal　that　the　addition　of　PPA　successfully　improves　the　processability,　hydrophilicity,　tensile　performance,　crystallization　and　elasticity　of　LLDPE.　This　work　therefore　not　only　expands　the　structural　and　functional　libraries　of　monomers　and　polymers　but　also　presents　a　novel　method　for　the　physical　modification　of　LLDPE　and　thus　might　inspire　advancements　in　the　fields　of　polymerization,　processing　and　modification　of　polyolefins.　©　2024　The　Royal　Society　of　Chemistry.