This review provides an in‐depth analysis of the electrical responses and relaxation behaviors of various polymeric materials including fiber‐reinforced polymer composites, polymer nanocomposites (PNC), and nanofiller‐reinforced polymeric films and coatings using dielectric spectroscopy (DS). The underlying theory of DS, corresponding instrumentation, various dielectric parameters, relevant equations, interpretations, and polarization mechanisms are thoroughly explored. The impact of synthetic and natural fibers and a diverse range of nanofillers on the dielectric responses and relaxation mechanisms of fiber‐reinforced composites, and PNC and films, respectively, are also examined. For each summarized article, we provide an overview of the composite or film preparation, followed by concise explanations of the dielectric behaviors under diverse conditions, including variations in temperature, frequency, moisture levels, fiber/filler ratios, and chemical treatment. In essence, this review contributes to a nuanced understanding of the intricate relationship between material structure, properties, and performance via DS data interpretation across a spectrum of scenarios.