The　ever　decreasing　amount　of　fossil　fuels　and　increasing　environmental　pollution　are　alarming　threats　for　green　and　sustainable　future.　Designing　a　new　catalyst　is,　therefore,　of　paramount　significance　in　the　quest　to　discover　sustainable,　robust,　and　environmentally　benign　materials　for　clean　and　sustainable　energy　generation.　Herein,　we　developed　a　hierarchically　oriented　catalyst　of　calcined　poly(ferrocenedimethano)-cyclotriphosphazene-microspheres　(CPFC-MS)　supported　with　nickel-aluminum　layered　double　hydroxide　and　decorated　with　nanoparticles　(NPs)　of　rhodium-nickel,　NiAl-LDH@RhxNi1-x　(x　=　2.06-6.75),　for　H2　generation　from　ammonia　borane　(AB)　hydrolysis.　The　highly　active　catalyst　was　characterized　by　scanning　electron　microscopy　(SEM),　Raman　spectroscopy,　high-resolution　transmission　electron　microscopy　(HRTEM)　and　TEM,　energy　dispersive　X-ray　spectroscopy　(EDX),　fourier　transform　infrared　(FTIR),　X-ray　diffraction　(XRD),　X-ray　photoelectron　spectroscopy　(XPS).　The　as-fabricated　CPFC-MS@NiAl-LDH@RhxNi1-x　(x　=　2.06-6.75)　catalysts　were　tested　for　AB　hydrolysis　and　the　results　showed　remarkable　performance　and　higher　stability　for　H2　generation.　The　CPFC-MS@NiAl-LDH@Rh2.06Ni7.32　catalyst,　having　the　lowest　Rh-contents,　exhibited　maximum　H2　generation　with　a　turn　over　frequency　(TOF)　of　780　mol　H2　hr-1　mol　Rh-1　and　an　activation　energy　(Ea)　of　40.3　kJ/mol　with　excellent　sustainability.　The　superior　activity　is　ascribed　to　the　synergetic　effect　between　RhNi　NPs　and　their　well-dispersion　over　hierarchically　oriented　CPFC-MS@NiAl-LDH　support,　while　higher　stability　due　to　LDH-AlNi/RhNi　attractions.　This　work　will　provide　new　opportunities　for　polyphosphazenes　and　LDH　derived　hierarchically　oriented　sustainable　catalysts　for　green　energy　production　for　sustainable　future.　©　2022　Elsevier　Ltd.