A　stable　and　conductive　interface　is　one　of　the　decisive　factors　in　manipulating　the　performance　of　high　voltage　LiNi0.5Mn1.5O4　(LNMO)　cathode　for　Li-ion　batteries.　Herein,　a　hybrid　Li3PO4-TiO2　coating　layer　is　designed　as　an　interfacial　material　via　controllable　atomic　layer　deposition　(ALD)　on　LNMO.　The　coating　acts　not　just　as　a　physical　barrier　to　prevent　the　side-reactions　between　cathode　and　electrolyte　at　high　voltage,　more　importantly,　the　hybrid　coating　material　improves　both　interfacial　ionic　and　electronic　conductivities　to　build　facile　Li-ion　and　electron　diffusion　pathways　for　LNMO.　The　optimized　LNMO　demonstrates　improved　rate　capability　and　long-life　stability.　The　capacity　retention　is　81.2%　comparing　with　47.4%　of　bare　LNMO　at　0.5C　after　300　cycles.　Detailed　surface　structural　evolution　is　studied　via　X-ray　absorption　near　edge　spectroscopy　and　transmission　electron　microscopy.　This　work　provides　new　insights　of　hybrid　interfacial　design　via　ALD　and　promotes　novel　electrode　architectures　for　batteries.