The homojunction of oxygen/metal vacancies and its interfacial n-p effect on the physiochemical properties are rarely reported. Interfacial n-p homojunctions of TiO are fabricated by directly decorating interfacial p-type titanium-defected TiO around n-type oxygen-defected TiO nanocrystals in amorphous-anatase homogeneous nanostructures. Experimental measurements and theoretical calculations on the cell lattice parameters show that the homojunction of oxygen and titanium vacancies changes the charge density of TiO ; a strong EPR signal caused by oxygen vacancies and an unreported strong titanium vacancies signal of 2D H TQ-SQ MAS NMR are present. Amorphous-anatase TiO shows significant performance regarding the photogeneration current, photocatalysis, and energy storage, owing to interfacial n-type to p-type conductivity with high charge mobility and less structural confinement of amorphous clusters. A new "homojunction of oxygen and titanium vacancies" concept, characteristics, and mechanism are proposed at an atomic-/nanoscale to clarify the generation of oxygen vacancies and titanium vacancies as well as the interface electron transfer.