Phosphorescent organic light-emitting diodes (PhOLEDs) have attracted intense attention owing to their theoretical 100% internal quantum efficiency through simultaneously utilizing singlet and triplet excitons. [1] With the tremendous efforts over the past few decades, the thermalevaporated electrophosphorescence devices with excellent external quantum efficiencies (EQEs) and operation lifetimes have been achieved. [2][3][4][5][6] Nevertheless, the development of high-efficiencies blue PhOLEDs remains as a daunting and forbidden challenge although blue emission is indispensable to improve color rendering index and color gamuts. [7][8][9][10][11][12] Moreover, the vacuum-deposited PhOLEDs require complicated technological processes and precisely controlling of concentrations of different materials in emission layer (EML) for realizing high device performance, which leads to relatively high fabrication costs. Solution-processed PhOLEDs based on spin-coating, blade coating and/or inkjet printing have been introduced with insistence because of their ultimate potential in facilitating largearea, low-cost, and high-efficiency flat-panel display as well as lighting products. [13,14] However, it is still quite difficult to develop solution-processed organic semiconductors simultaneously with the characteristics of good-solubility, large bandgap, and good carrier transportation for high-performance solutionprocessed blue PhOLEDs, which are fundamentally important for next-generation lighting sources and displays technologies.Commonly, the host-dopant systems are generally adopted to controllably eliminate the triplet-involved quench effects of emissive phosphors in the PhOLEDs. [15] The basic metrics of solution-processed hosts are excellent electrical property for endowing efficient and balanced carrier injection and flux, and high triplet energy (E T ) levels for maintaining exothermic energy migration from the hosts to dopants and confining the triplet excitons in EML. [16,17] Furthermore, additional requirements of hosts have to be simultaneously fulfilled to support high-efficiency solution-processed PhOLEDs: [18,19] i) good solubility in common organic solvent to fabricate stable, uniform and pin-hole free films, ii) high thermal and chemical stability to endow high temperature thermal annealing for eliminating Selectively and controllably regulating molecular functions of organic optoelectronic materials with high solubility for solution-processible devices is highly desired but remains as one of the most significant challenges in material science. Here, a concise molecular design strategy is reported to achieve effective electronic communications using efficient d-orbital participated σ-π conjugations between Si and π unit for purposely modulating the electrical properties of organic optoelectronic materials. Through a two-step reaction in high yield, DSiDCzSi with the enhanced σ-π conjugation is facilely constructed by introducing multiple triphenylsilanes into carbazole unit. Impressively, DSiD-CzSi demonstrates...