Bowl-like　structures　have　great　potential　in　the　field　of　catalysis,　environmental　remediation,　energy　storage,　etc.,　because　of　the　large　surface　area,　porous　structure,　and　buffer　hollow　space.　Herein,　we　developed　a　unique　approach　to　control　the　opening　direction　of　bowl-like　structures　via　self-assembly　strategy　at　the　gas/liquid　interface　of　liquid　B2O3　environment　foam.　BN@BPO4　self-supporting　monolithic　foam　with　oriented　bowl-like　structure　was　obtained,　which　is　built　by　numerous　oriented　bowl-like　blocks　and　shows　a　double　layer　structure　with　face-to-face　opening.　The　opening　size　can　be　adjusted　by　changing　the　amount　of　Cu(NO3)2　additives　that　is　beneficial　for　the　production　of　hexagonal　boron　nitride　(h-BN).　We　believe　the　as-generated　h-BN　can　enhance　the　gas　trapping　capacity　of　liquid　B2O3　environment　foam　to　precisely　control　pressure　differential　between　large　and　small　bubbles　and　thus　favors　the　oriented　opening　of　bowl-like　structure.　Further,　pure　h-BN　monolithic　foam　with　oriented　bowl-like　structure　prepared　at　higher　temperature　possessed　multimodal　hier-archically　porous　structure　and　excellent　performance　in　the　catalytic　oxidative　dehydrogenation　of　propane　into　propene　and　the　removal　of　organic　pollutants.　This　work　provides　an　extended　assembly　interface　strategy　of　oriented　bowl-like　structure　materials　for　different　applications.