In this work, a polymer and ionic liquid (IL) hybrid with superior thermoelectric performance is prepared via a system design of the chemical composition, molar ratio of the constituent molecules and manipulating the structure in solution and dried films. The solution-casted hybrid film, consisting of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and 1-ethyl-3-methylimidazolium tricyanomethanide (EMIM:TCM), shows the highest power factor of 175 μW m⁻¹ K⁻²in the polymer hybrid prepared by a post-treatment-free method. With a set of complementary structure characterization methods, it is found that EMIM:TCM can induce the structure reorganization of PEDOT:PSS in solution from a core-shell model to a rod-like model, during which PEDOT partially separates from PSS that eases the conductive network formation. In addition, the oxidation level of PEDOT:PSS is reduced by adding EMIM:TCM. Based on which, the PEDOT:PSS/IL hybrid shows the best performance in optimizing the conductivity (1163 S cm⁻¹) and Seebeck coefficient (38.8 μV K⁻¹) simultaneously.

Pure and Nb‐doped TiO₂ photocatalysts with highly ordered alternating gyroid architecture and well‐controllable mesopore size of 15 nm via co‐assembly of a poly(isoprene)‐block‐poly(styrene)‐block‐poly(ethylene oxide) block copolymer are synthesized. A combined effort by electron microscopy, X‐ray scattering, photoluminescence, X‐ray photoelectron spectroscopy, Raman spectroscopy, and density functional theory simulations reveals that the addition of small amounts of Nb results in the substitution of Ti⁴⁺ with isolated Nb⁵⁺ species that introduces inter‐bandgap states, while at high concentrations, Nb prefers to cluster forming shallow trap states within the conduction band minimum of TiO₂. The gyroidal photocatalysts are remarkably active toward hydrogen evolution under UV and visible light due to the open 3D network, where large mesopores ensure efficient pore diffusion and high photon harvesting. The gyroids yield unprecedented high evolution rates beyond 1000 µmol h⁻¹ (per 10 mg catalyst), outperforming even the benchmark P25‐TiO₂ more than fivefold. Under UV light, the Nb‐doping reduces the activity due to the introduction of charge recombination centers, while the activity in the visible triple upon incorporation is owed to a more efficient absorption due to inter‐bandgap states. This unique pore architecture may further offer hitherto undiscovered optical benefits to photocatalysis, related to chiral and metamaterial‐like behavior, which will stimulate further studies focusing on novel light–matter interactions.