Isomerization　of　alkane　is　one　of　the　most　important　catalytic　processes　for　producing　environmentally　friendly　gasoline　fraction　with　high　octane　number.　However,　the　development　of　non-noble　metal　based　catalysts　with　high　conversion　and　selectivity　towards　multi-branched　isomerized　products　is　still　challenging.　Herein,　we　report　that　a　NiP-Hβ/modified　Kaolin　catalyst　was　successfully　prepared　by　ball-milling　of　amorphous　NiP　nanoparticles　with　Hβ/modified　Kaolin　composites　and　applied　for　n-hexane　isomerization.　The　introduction　of　chemically　modified　Kaolin　with　abundant　weak-medium　acid　sites　and　mesopores　not　only　alleviates　the　cracking　of　isomerized　products　on　the　strong　acid　sites　on　Hβ,　but　also　provides　more　active　sites　for　the　formation　of　di-branched　isomerized　products　with　high　octane　number.　As　a　result,　the　NiP-Hβ/modified　Kaolin　catalyst　shows　an　excellent　catalytic　performance　for　n-hexane　isomerization　in　terms　of　good　conversion　(78.1%),　high　selectivity　towards　mono-branched　(75.4%)　and　di-branched　(21.4%)　i-C6　products,　and　high　liquid　yield　(99.9%).　This　work　paves　the　way　to　the　development　of　high　performance　non-noble　metal　based　catalysts　for　large　scale　production　of　clean　gasoline.　©　2022　Elsevier　Ltd