A cementitious paste fill (CPF) ensures the long-age stability of underground cavities. Recently, superplasticizers, specifically ones that are polycarboxylate ether-based, have been incorporated to enhance CPF performance, yet their long-term effects on permeability, mechanical properties, and microstructures remain unclear. This study investigates these effects with CPF samples containing varying superplasticizer dosages (0%, 1%, 3%, 5%) that have been cured for up to 150 days. Rheological assessments (slump cone, vane shear tests), unconfined compressive strength testing, microstructural characterization (MIP, SEM), and hydraulic conductivity measurements were performed alongside XRD and thermal analyses (TAns) on high w/c (2) cement paste samples. The results showed that superplasticizer addition reduced CPF water content by 23% and yield stress by six times, aiding slurry transport. Long-term strength was enhanced by up to 2.4 times compared to the control samples, indicating improved underground stability. Superplasticizers altered the CPF samples stress–strain responses, increasing their load-bearing capacity. TG/DTG and XRD analyses revealed that hydration product development increased and porosity decreased in the presence of a superplasticizer. Hydraulic conductivity and permeability also decreased significantly. SEM and MIP analyses showed that the superplasticizer enhanced denser microstructures with fewer pores and fractures. These findings offer promising implications for designing CPFs with improved strength, durability, and environmental sustainability.