Solid-phase molecular self-assembly (SPMSA) is emerging as an efficient approach, leading to scale-span self-assembled supramolecular films. With SPMSA, freestanding macroscopic supramolecular films can be formed upon mechanically pressing the precipitates formed with polyelectrolytes and oppositely charged surfactants. Herein, we report that the film formation ability and the mechanical strength of the resultant film depend highly on the surfactant chain lengths and the molecular weight of polyelectrolytes. A coarse-grained molecular dynamics study revealed that the longer surfactant chains are beneficial for the ordered assembly of surfactant bilayers in the film, whereas the larger molecular weight of PE favors the enhanced mechanical strength of the film by promoting the long-range order of the surfactant bilayers. The current results disclosed the physical insight of the surfactant chain length and the molecular weight of polyelectrolytes into the film structure and mechanical strength, which is of practical importance in guiding the creation of SPMSA materials.