Triptycene derivatives bearing lengthy alkoxy chains on the 1,8,13- or 1,8-positions have been demonstrated to self-assemble on stable substrates into extremely ordered skinny movies that includes a two-dimensional (2D) nested hexagonal packing of the triptycene moieties and a one-dimensional (1D) stacking layer. Though the bulk-phase buildings of those derivatives have been clarified, the molecular-level mechanism governing their meeting close to stable interfaces stays elusive. Right here, we carried out all-atom molecular dynamics (MD) simulations to analyze three triptycene derivatives (Trip1, Trip2, and Trip3) with totally different alkoxy-chain substitution patterns, revealing their meeting buildings, thermodynamic stabilities, and interfacial ordering processes. Our simulations confirmed that antiparallel molecular alignment is thermodynamically steady in bulk assemblies, whereas skinny movies preferentially undertake a parallel alignment, indicating that stable interfaces promote this orientation. Moreover, thermal annealing of stair-stepped trilayers drove their transformation into flat bilayers and the expansion of hexagonally ordered domains, quantified by radial distribution capabilities and hexatic order parameters. Comparative evaluation demonstrated that alkoxy substitution patterns dictate packing density, structural order, and section stability, in wonderful settlement with experimental observations. These findings present molecular-level insights into interface-driven self-assembly and set up design rules for establishing thermodynamically steady, extremely ordered natural skinny movies, enabling simulation-guided methods for next-generation nanoscale supplies design.