Deployment-oriented technology pathway assessment is increasingly important for large-scale energy storage, because technology selection must consider not only theoretical performance but also site constraints and maturity-related feasibility. This study proposes an integrated Site–Performance–Technology Maturity (S–4E–T) framework as a general architecture for deployment-oriented technology pathway assessment. The framework links site suitability, multidimensional 4E performance evaluation, namely energy, exergy, exergoeconomic, and exergoenvironmental analyses, technology maturity quantification, maturity-based realism correction, and AHP–TOPSIS decision analysis. It is demonstrated for five representative salt-cavern pathways, including C-CAES, A-CAES, HH-CAES, HES-GT, and HES-FC, under unified site-derived boundaries from the Pingdingshan case. Results show that A-CAES has clear thermodynamic and economic advantages, while HES-FC exhibits the lowest environmental impact and strong theoretical competitiveness. A clear maturity gradient is identified, ranging from TRL 9 for C-CAES to TRL 5 for HH-CAES. Before maturity correction, the TOPSIS ranking is HES-FC > A-CAES > HH-CAES > C-CAES > HES-GT; after correction, it changes to A-CAES > HES-FC > C-CAES > HH-CAES > HES-GT. Scenario analysis further indicates that C-CAES is favored under maturity priority, whereas hydrogen-coupled pathways, especially HH-CAES, become more attractive under fast-response flexibility priority. Overall, the proposed framework enables physically consistent and maturity-aware cross-pathway comparison and supports stage-specific planning of salt-cavern energy storage toward 2040.