In this paper, over 1.1 eV continuous tuning of metal oxides workfunction is realized by cesium intercalation, making the metal oxide function as both electron transport layer and hole transport layer in organic optoelectronic devices. The demonstrated metal oxides are commonly used molybdenum oxide and vanadium oxide. The proposed approach of synthesizing cesium intercalated metal oxides has interesting properties of room-temperature, ambient atmosphere, water free and solution process, favoring the formation of metal oxides as carrier transport layers at different regions in multilayered devices and large scale fabrication of organic optoelectronics at low cost. Besides the wide range of controllable workfunction adjustment, band structures, and electrical properties are investigated in detail, to understand the effects of cesium intercalation on metal oxides. The device results show that, using the proposed cesium intercalation approach, each of the two investigated metal oxides can function as both ETL and HTL in organic solar cells and organic light emitting diodes with very good device performances. Consequently, with the interesting properties in film synthesis, the proposed cesium intercalated metal oxides can achieve continuously workfunction tuning over a large range and contribute to evolution of the simple route for fabricating high performance organic optoelectronic devices.