Conspectus The controlled doping of organic semiconductors (OSCs) is crucial not only for improving the performance of electronic and optoelectronic devices but also for enabling efficient thermoelectric conversion and spintronic applications. The mechanism of doping for OSCs is fundamentally different from that of their inorganic counterparts. In particular, the interplay between dopants and host materials is complicated considering the low dielectric constant, strong lattice-charge interaction, and flexible nature of materials. Recent experimental breakthroughs in the molecular design of dopants and the precise doping with high spatial resolution call for more profound understandings as to how the dopant interacts with the charge introduced to OSCs and how the admixture of dopants alters the electronic properties of host materials before one can exploit controllable doping to realize desired functionalities. By employing state-of-the-art computational tools, we revealed the effects of doping in representative and emerging organic and coordination polymers aiming toward thermoelectric and spintronic applications. We showed that dopants and hosts should be taken as an integrated system, and the type of charge-transfer interaction between them is the key for spin polarization. First, we found doping-induced modifications to the electronic band in a potassium-doped coordination polymer, an n-type thermoelectric material. The charge localization due to the Coulomb interaction between the completely ionized dopant and the injected charge on the polymer backbone and also the polaron band formation at low doping levels are responsible for the nonmonotonic temperature dependence of the conductivity and Seebeck coefficient observed in recent experiments. The mechanistic insights gained from these results have provided important guidelines on how to control the doping level and working temperature to achieve a high thermoelectric conversion efficiency. Next, we demonstrated that the ionized dopants scatter charge carriers via screened Coulomb interactions, and it may become a dominant scattering mechanism in doped polymers. After incorporating the ionized dopant scattering mechanism in PEDOT:Tos, a p-type thermoelectric polymer, we were able to reproduce the measured Seebeck coefficient-electrical conductivity relationship spanning a wide range of doping levels, highlighting the importance of ionized dopant scattering in charge transport. In the two cases described above, charge injection is enabled by integral charge transfer between the dopant and host polymers. In a third example, we showed that a novel type of stacked two-dimensional polymer, conjugated covalent organic frameworks (COFs) with closed-shell electronic structures, can be spin polarized by iodine doping via fractional charge transfer even at high doping levels. We then manifested that magnetization can be attained in nonmagnetic materials lacking metal d electrons and further designed two new COFs with tunable spintronic structure and magnetic interactions after the iodine doping. These findings have suggested a practical route to enable spin polarization in nonradical materials by chemical doping via orbital hybridization, which holds great promise for flexible spintronic applications.