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Background Sexual dysfunction following radical prostatectomy remains a persistent challenge affecting patient quality of life. Health literacy may influence engagement with multimodal rehabilitation strategies, yet its role in sexual health recovery practices remains poorly understood, particularly in non-Western populations. Methods This single-center cross-sectional Knowledge-Attitudes-Practices survey was conducted at a tertiary urology center in China from March 2023 through June 2025. We enrolled 1,615 men following radical prostatectomy and collected partner-reported items where available, stratifying participants by health literacy tertiles, using the validated HLS19-Q12 instrument. Primary outcomes included knowledge scores, treatment utilization (PDE5 inhibitors, vacuum devices, injection therapy, pelvic floor training), multimodal engagement, and adherence rates. Statistical analyses employed hierarchical logistic regression, mediation analysis, and latent class modeling. Results Among 1,615 men (low n = 538; moderate n = 539; high n = 538), higher (vs low) health literacy was associated with greater PDE5 inhibitor use (adjusted OR 1.42; 95% CI: 1.08–1.86; p = 0.01), injection therapy utilization (adjusted OR 1.58; 95% CI: 1.16–2.15; p = 0.004), multimodal engagement (≥2 modalities: adjusted OR 1.56; 95% CI: 1.18–2.06; p = 0.002), and adherence ≥80% (adjusted OR 1.71; 95% CI: 1.30–2.25; p < 0.001). Structural equation modeling indicated that health literacy was statistically associated with an indirect pathway consistent with partial mediation of the knowledge and practice association (proportion mediated 0.31; 95% CI: 0.18–0.49; p < 0.001). Treatment barriers decreased systematically: side effect concerns (44.1% vs. 28.1%, OR 0.51, p < 0.001), embarrassment (35.1% vs. 20.8%, OR 0.49, p < 0.001), and cost concerns (49.1% vs. 32.3%, OR 0.50, p < 0.001). Information-seeking behaviors increased dramatically with higher literacy: active health information seeking (35.1% vs. 66.2%, OR 3.64, p < 0.001) and digital resource use (27.0% vs. 61.2%, OR 4.27, p < 0.001). Latent class–based risk stratification identified a high-risk class comprising 22% of participants who may benefit from immediate intervention. Conclusion Health literacy is a fundamental, modifiable correlation of post-prostatectomy sexual recovery, demonstrating statistical associations consistent with knowledge to practice mediation pathways. Cross-sectional findings reveal substantial literacy-stratified disparities in treatment utilization and adherence, warranting prospective trials of routine health literacy assessment and tiered intervention strategies to reduce inequities and improve sexual health outcomes.