Manganese　oxide　composites　with　mixed　valence　states　were　prepared　through　the　hydrothermal　method　by　compositing　with　Ti4O7　and　calcining　at　different　temperatures,　and　their　ORR　and　OER　catalytic　performance　were　investigated.　The　prepared　catalysts　were　characterized　by　XRD,　SEM-EDS,　HRTEM-EDS,　and　XPS　methods　to　analyse　their　phase　constitution,　morphology　feature,　and　surface　composition.　The　major　phase　of　manganese　oxides　was　Mn3O4,　which　is　a　one-dimensional　structure,　and　its　growth　was　induced　by　Ti4O7.　The　ORR　and　OER　catalytic　activity　can　be　enhanced　due　to　the　preferred　orientation　of　manganese　oxides.　Electrochemical　measurements,　namely　CV,　LSV　and　EIS,　were　utilized　for　determining　the　ORR　and　OER　catalytic　activity,　whereas　CA　and　ADT　were　used　for　studying　the　durability　and　stability.　A　Li-O2　battery　was　assembled　to　test　the　electrochemical　behavior　and　properties　in　practical　application.　MnOx/Ti4O7　calcined　at　300　°C　exhibited　the　best　catalytic　activity　of　0.72　V　vs.　RHE　half-wave　potential　for　ORR　and　0.67　V　vs.　RHE　overpotential　for　OER.　The　proportion　of　Mn3+　was　also　highest　in　all　the　MnOx/Ti4O7　composites.　The　assembled　Li-O2　battery　shows　high　performance　with　a　voltage　gap　of　only　0.85　V.　Therefore,　it　can　be　affirmed　that　the　inducement　of　Ti4O7　could　strengthen　the　preferred　orientation　in　manganese　oxide　growth　and　Mn3+　in　MnOx/Ti4O7　plays　a　vital　role　in　catalyzing　ORR　and　OER,　with　both　improving　the　ORR　and　OER　bifunctional　catalytic　performance　of　manganese　oxides.　©　The　Royal　Society　of　Chemistry.