Nanostructured lipid carrier represents a cutting-edge drug delivery platform, offering enhanced encapsulation of lipophilic agents, high drug loading, controlled release, and superior skin hydration effects due to occlusive properties. This study aimed to develop gel-based NLC formulations by co-encapsulation of α-Tocopherol and α-Tocopheryl acetate (TTA) for enhanced anti-aging performance. Six formulations (TTA1–TTA6) were prepared using varying concentrations of solid and liquid lipids (lauric acid and oleic acid) and surfactant (Tween 80) with one placebo formulation (TTA0). NLC formulations were fabricated via hot melt encapsulation method and optimized based on particle size, polydispersity index, and entrapment efficiency. The best optimised formulation underwent detailed characterization, including Dynamic Light Scattering, Fourier Transform Infrared Spectroscopy, X-ray Diffraction, Differential Scanning Calorimetry, and Thermo Gravimetric Analysis. All formulations showed high encapsulation efficiency (66–93%), particle sizes ranging from 68–290 nm, spherical morphology, and thermal stability. A two-phase release profile was seen, including burst and then sustained release. Comparative in vitro and ex vivo evaluations of gels confirmed superior skin retention and minimal transdermal permeation. In vivo testing on human volunteers revealed significantly enhanced moisture retention (up to 68%) and improved skin elasticity for gel-based NLC formulations (TTA2G) as compared to solution gel (TTAsolG). These results confirm the synergistic potential of co-encapsulation of TTA in nanostructured lipid carriers to improve topical delivery and anti-aging outcomes.