Oxide　semiconductors　are　key　materials　in　many　technologies　from　flat-panel　displays?solar　cells　to　transparent　electronics.　However,　many　potential　applications　are　hindered　by　the　lack　of　high　mobility　p-type　oxide　semiconductors　due　to　the　localized　O-2p　derived　valence　band　(VB)　structure.　In　this　work,　the　VB　structure　modulation　is　reported　for　perovskite　Ba2BiMO6　(M　=　Bi,　Nb,　Ta)　via　the　Bi　6s(2)　lone　pair　state　to　achieve　p-type　oxide　semiconductors　with　high　hole　mobility　up　to　21　cm(2)　V-1　s(-1),　and　optical　bandgaps　widely　varying　from　1.5　to　3.2　eV.　Pulsed　laser　deposition　is　used　to　grow　high　quality　epitaxial　thin　films.　Synergistic　combination　of　hard　x-ray　photoemission,　x-ray　absorption　spectroscopies,　and　density　functional　theory　calculations　are　used　to　gain　insight　into　the　electronic　structure　of　Ba2BiMO6.　The　high　mobility　is　attributed　to　the　highly　dispersive　VB　edges　contributed　from　the　strong　coupling　of　Bi　6s　with　O　2p　at　the　top　of　VB　that　lead　to　low　hole　effective　masses　(0.4-0.7　m(e)).　Large　variation　in　bandgaps　results　from　the　change　in　the　energy　positions　of　unoccupied　Bi　6s　orbital　or　Nb/Ta　d　orbitals　that　form　the　bottom　of　conduction　band.　P-N　junction　diode　constructed　with　p-type　Ba2BiTaO6　and　n-type　Nb　doped　SrTiO3　exhibits　high　rectifying　ratio　of　1.3　x　10(4)　at　+/-　3　V,　showing　great　potential　in　fabricating　high-quality　devices.　This　work　provides　deep　insight　into　the　electronic　structure　of　Bi3+　based　perovskites　and　guides　the　development　of　new　p-type　oxide　semiconductors.