The mechanical properties of Ti alloys are significantly affected by the introduction of solute or impurity elements. Thus, the role of impurities on the hardening or softening behavior of α-Ti was investigated through first principles calculations. In particularly, to provide a comprehensive electronic and atomic basis of solute addition in α-Ti, the effect of metallic (V and Al) and non-metallic (C and O) impurities on the ideal shear strength (ISS) and generalized stacking fault energy (GSFE) across different slip systems of Ti were probed. The results revealed that the addition of V atom reduces both ISS and unstable stacking fault energy across various slip systems of α-Ti, whereas Al addition increases the ISS of Ti. Further, the addition of O atom decreases ISS for most of the slip systems while C solute atom increases ISS across all slip systems of α-Ti. To illustrate the underlying factors influencing the observed softening/strengthening behavior, the electronic density of states and valence charge transfer were determined. The electronic density of states calculations showed that the contribution from the d states of V atom decreases the stability of Ti-V solid solution, thereby leading to a decrease in the plastic anisotropy of α-Ti. Finally, the shearability parameter and critical resolved shear stress (CRSS) ratios across different slip systems of Ti solid solutions were calculated to understand the macroscopic effects of impurity addition on the deformation behavior of α-Ti at ambient conditions. Overall, the first-principles study provides an insight into the electronic basis of strengthening/softening effect of solute addition in α-Ti and assesses their implications on the deformation behavior of α-Ti alloys.