A　template　free　synthesis　route　was　developed　for　the　synthesis　of　hierarchical　zeolite　Beta　from　a　natural　layered　aluminosilicate　mineral　kaolin.　Detailed　study　on　the　crystallization　of　zeolite　Beta　established　the　optimized　synthesis　condition,　and　the　synthesized　hierarchical　Beta　zeolite　was　fully　studied　by　XRD,　IR,　SEM,　TEM,　BET,　NH3-TPD,　Py-IR　and　NMR　techniques.　The　characterization　results　reveal　that　the　hierarchical　Beta　zeolite　possesses　good　crystallinity,　bimodal　pore　architecture,　large　surface　area,　big　pore　volume,　high　acid　site　concentration　and　excellent　hydrothermal　stability.　An　improved　catalytic　performance　was　achieved　in　hierarchical　Beta　zeolite　for　the　esterification　of　acetic　acid　with　benzyl　alcohol,　and　the　high　activity　and　selectivity　in　this　zeolite　are　mainly　attributed　to　the　presence　of　mesopores　for　accelerating　the　intraparticle　diffusion　rate　of　both　reactant　and　product.　This　novel　synthesis　methodology　provides　a　low-cost　and　environmentally-benign　way　for　the　preparation　of　hierarchical　Beta　zeolite,　which　could　serve　a　sustainable　platform　of　large-scale　production　of　hierarchical　zeolite　for　practical　application.