High-work function transparent electrodes (HWFTEs) are key for establishing Schottky and Ohmic contacts with n-type and p-type semiconductors, respectively. However, the development of printable materials that combine high transmittance, low sheet resistance, and tunable work function remains an outstanding challenge. This work reports a high-performance HWFTE composed of Ag nanowires enveloped conformally by Ti3C2Tx nanosheets (TA), forming a shell-core network structure. The printed TA HWFTEs display an ultrahigh transmittance (>94%) from the deep-ultraviolet (DUV) to the entire visible spectral region, a low sheet resistance (<15 Ωsq-1), and a tunable work function ranging from 4.7 to 6.0eV. The introduction of additional oxygen terminations on the Ti3C2Tx surface generates positive dipoles, which not only increases the work function of the TA HWFTEs but also elevates the TA/Ga2O3 Schottky barrier, resulting in a high self-powered responsivity of 18mAW-1 in Ga2O3 diode DUV photodetectors, as demonstrated via experimental characterizations and theoretical calculations. Furthermore, the TA HWFTEs-based organic light-emitting transistors exhibit exceptional emission brightness of 5020cd m-2, being four-fold greater than that in Au electrodes-based devices. The innovative nano-structure design, work function tuning, and the revealed mechanisms of electrode-semiconductor contact physics constitute a substantial advancement in high-performance optoelectronic technology.