We　describe　a　simple,　efficient　plasma-chemical　technique　for　the　synthesis　of　hybrid　structures　formed　by　vertically　oriented　BNCO　nanowalls　and　vertically　oriented　graphene　nanoflakes　(BNCONW/GNFs),　as　well　as　their　structure　and　photoluminescence　properties.　The　BNCONW/GNF　hybrid　structures　were　fabricated　by　the　synthesis　of　vertically　oriented　BNCO　nanowalls　in　N-2-H-2　plasma　using　the　plasma-enhanced　hot　filament　chemical　vapour　deposition　technique,　followed　by　the　direct　synthesis　of　vertically　oriented　graphene　nanoflakes　on　the　BNCO　nanowalls　in　a　methane　environment　using　a　hot　filament　chemical　vapour　deposition　method,　where　the　B4C　compound　was　used　as　the　boron　and　carbon　source.　The　results　of　field　emission　scanning　electron　microscopy,　transmission　electron　microscopy,　micro-Raman　spectroscopy　and　X-ray　photoelectron　spectrometry　measurements　indicated　that　the　BNCONW/GNF　hybrid　structures　were　composed　of　vertically　oriented　BNCO　nanowalls　and　vertically　oriented　graphene　nanoflakes.　The　photoluminescence　studies　of　the　vertically　oriented　BNCONW/GNF　hybrid　structures　using　a　Ramalog　system　equipped　with　a　325　nm　He-Cd　laser　demonstrated　the　possibility　to　efficiently　tune　the　photoluminescence　properties　of　the　BNCONW/GNF　structures　by　growing　the　graphene　nanoflakes　on　the　vertically　oriented　BNCONWs.　Our　findings　can　contribute　to　the　designing　of　complex　hybrid　graphene-semiconductor　structures　suitable　for　applications　in　advanced　next-generation　optoelectronic　nanodevices.