Lithium-sulfur (Li-S) batteries are among the most promising next-generation energy storage systems that have the potential to surpass traditional lithium-ion batteries in terms of both energy density and cost. These batteries are composed of a lithium anode and a sulfur cathode and operate through a redox reaction in which lithium ions are transferred between the two electrodes. This reaction allows lithium-sulfur batteries to store more energy per unit weight than lithium-ion batteries, making them an attractive option for a wide range of applications. However, despite their potential advantages, Li-S batteries have faced several challenges in terms of their performance and stability, such as the insulating nature of the elemental sulfur and the shuttle effect of dissolvable lithium polysulfides. Conjugated polymers is a class of polymeric materials that exhibits alternating single and double bonds in their main chain, which gives them unique electrical, optical, and mechanical properties. In the context of Li-S batteries, conjugated polymers can be used as cathode material to improve the electrical conductivity of the sulfur cathode and to prevent the dissolution of the active materials by forming strong chemical bonds with sulfur. Among these, thiol-containing polymers are one example where the -SH groups can be cross-linked with sulfur via covalent bonding. In a recent study, we presented a new fabrication strategy to construct a binder-and carbon additive-free organosulfur cathode based on a thiol-containing conducting polymer poly(4-(thiophene-3-yl)benzenethiol) (PTBT). The PTBT features the polythiophene main chain as a highly conducting framework and the benzenethiol side chain to copolymerize with sulfur and form a cross-linked organosulfur polymer. We have been able to show the significant fixing effect of sulfur species by operando X-ray imaging. This synthesis approach maintains the conductivity and flexibility of the polymer framework and therefore seems promising to overcome typical drawbacks of Li-S batteries. In a further study, we used a combination of first-principles computational methods and statistical mechanics to explore the structural characteristics of the initial state of a vulcanized PTBT polymer. Our calcu-lations showed that the main reaction of the vulcanization process leads to high-probability states of sulfur chains cross-linking TBT units belonging to different polymer backbones, with a dominant sulfur chain length of 5 atoms. Similar results have been reported for different sulfur/carbon copolymers. The morphology of a polymer can greatly impact its conductive behavior. In general, polymers with more ordered and aligned structures allow for more efficient transport of charges and tend to have higher conductivity than those with disordered structures. The morphology of the polymer can be controlled through various synthesis techniques. Understanding the relationship between morphology and conductivity can allow for the design of polymers with improved conductive behavior. Thiophene-based conjugated polymers such as the well-known poly(3-hexylthiophene) (P3HT), poly(2,5-bis(3-alkylthiophen-2yl)thieno[3,2-b]-thiophene) (PBTTT), or poly-3,4-ethylendioxythiophen (PEDOT) have been extensively studied over the last decades to demonstrate morphology-transport relationships, but many fundamental questions in this field of polymeric organic semiconductors remain unanswered. One important factor influencing the charge transport properties of all of these systems is the regioregularity of their backbones. In order to elucidate this relationship for our novel PTBT polymer from a theoretical point of view, the knowledge of an accurate atomistic model of the material is crucial for a structural description and the calculation of its electronic properties. In this work, we employ classical molecular dynamics (MD) simulations to explore the self-assembly process of conjugated PTBT chains of different backbone regularities. To validate our structure predictions, we compare experimental X-ray diffraction (XRD) measurements of the electropolymerized PTBT polymer with simulated diffraction patterns. Taking the generated structures as input, we then use electronic structure theory to investigate how the structural changes of the polymer influence its electronic and charge transport properties. Finally, we employ Boltzmann transport and deformation potential theory as a quantitative approach to estimating the intrinsic transport limit of the PTBT polymer.