Ideally, balanced transport for both hole and electron carriers is favored in these double-carrier devices. But in actual, there is still a big lag between the electron and hole transport properties. For instance, the extremely high hole mobility has reached much more than 20 cm 2 V −1 s −1 , [10][11][12][13][14] but in sharp contrast, very few literatures have reported electron mobility beyond 10 cm 2 V −1 s −1 . [15][16][17][18][19] Understanding the determining factors that limit the charge mobility, especially for electron transport, is significant yet challenging. Several typical obstacles to electron conductance, such as the high electron injection barriers [20][21][22] and the electron traps at the semiconductor-dielectric interface, [23] have been widely studied. The polarity of dielectric layer, consisting of a set of dipoles, [24] has another crucial effect. In 2003, Veres et al. observed that charge transport showed strong correlation with dielectric polarizability and they put forward that the dielectric layer could change the density of states by local polarization effects and thus affect the charge transport and indeed, carrier localization is enhanced by insulators with larger permittivity. [22,25] The dominant mechanism is the so-called dipolar disorder. [25][26][27][28] Hulea et al. carried on measurements on rubrene single-crystal devices for the observation of intrinsic charge-transport characteristics and reported that the mobility dependence on dielectric polarizability has a dynamic origin owing to the coupling of the charged carriers in the organic conducting channel to the ionic lattice of the dielectric. [29] This coupled carrier-polarization cloud is referred to as a "Fröhlich polaron" [30][31][32] and moves with electron (or hole). The authors also demonstrated that the charge mobility would switch from a band-like character to a hopping one when the dielectric polarizability increased. In addition to the polarity of dielectrics, we further found that the polarity effects could arise from the solvent residues in solution-processed organic semiconductors. In fact, the existence of polar solvent residues is identified as a factor detrimental to electron transport. [15,33] Both of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene), and an n-type material, 6,13-bis(triisopropyl silylethynyl)-5,7,12,14-tetraazapentacene (TIPS-TAP), have been examined. Crystals of TIPS-pentacene grown from non-polar solvents exhibited ambipolar transport for the first time with Balanced electron and hole transport properties are essential for various organic electrical/optoelectrical applications such as organic solar cells, complementary circuits, and light-emitting transistors. However, the electron transport in organic semiconductor lags far behind the hole side, making it with vital significance to seek the factors that limit the electron mobility. Here, the authors demonstrate that the π-conjugated solvents, as essential components in the widely-used solution processing techniques, can signific...