Integrating　two-dimensional　ultra-wide　band　gap　hexagonal　boron　nitride　(h-BN)　on　β-Ga2O3　surface　into　van　der　Waals　heterostructures　is　of　great　interest　for　developing　novel　high-power　devices　and　optoelectronic　devices　because　of　their　unique　properties.　The　energy　band　alignment　at　the　heterointerface　is　critical　for　device　design,　however,　the　band　alignment　of　h-BN/β-Ga2O3　heterojunction　has　not　been　investigated　to　date.　In　this　work,　the　h-BN/β-Ga2O3　heterostructure　is　constructed　by　directly　growing　h-BN　few-layer　on　the　β-Ga2O3　single　crystal　substrate　using　ion　beam　sputtering　deposition　method.　The　high-quality　few-layer　h-BN　with　the　abrupt　interface　and　smooth　surface　allow　for　the　accurate　determination　of　band　alignment　at　the　h-BN/β-Ga2O3　heterointerface　by　X-ray　photoelectron　spectroscopies.　The　valence　and　conduction　band　offsets　are　determined　to　be　0.47　and　1.42　eV　for　the　h-BN/β-Ga2O3　heterostructure,　respectively,　with　a　type-　staggered　band　alignment.　Furthermore,　the　electronic　structures　of　h-BN/β-Ga2O3　heterostructure　are　also　investigated　experimentally　and　theoretically.　These　results　indicate　that　the　h-BN/β-Ga2O3　heterostructure　has　great　potential　in　(opto)electronic　devices.　©　2022　Elsevier　B.V.