The growing demand for advanced energy storage systems requires the development of next-generation battery technologies with superior energy density and cycle stability, with lithium-sulfur (Li-S) batteries representing a promising solution. Sulfur-containing polyacrylonitrile cathodes (SPAN) for Li-S batteries are a significant advancement for this next-generation battery chemistry, addressing the major issue of limited cycle life encountered in conventional carbon/sulfur composite cathodes. In the presented study, the influence of available ionic and electronic conduction pathways within the cathode on the electrochemical performance of SPAN-based Li-S batteries is studied in details. To this end, a series of SPAN cathodes with different microstructures is prepared by adapting the compression degree of calendering. Mechanical and morphological characterizations confirm a pronounced springback effect due to a characteristic elastic deformation behavior of SPAN. Electrochemical impedance spectroscopy (EIS) shows increased cathode impedance values with multiple overlapping processes in the high- to mid-frequency region in highly compressed SPAN cathodes. Moreover, while the (first) discharge capacity is unaffected, the subsequent charge capacity decreases substantially for highly compressed cathodes. The electrochemical experiments and electrochemical continuum simulations confirm that this phenomenon is mainly due to the disturbance of the electronic percolation pathways caused by the springback behavior during calendering.