The separation of haloalkane isomers with distillation-free strategies is one of the most challenging research topics in fundamental research and also gave high guiding values to practical industrial applications. Here, this contribution provides a previously unidentified solid supramolecular adsorption material based on a leggero pillararene derivative BrP[5]L, which can separate 1-/2-bromoalkane isomers with near-ideal selectivity. Activated solids of BrP[5]L with interesting amorphous and nonporous features could adsorb 1-bromopropane and 1-bromobutane from the corresponding equal volume mixtures of 1-/2-positional isomers with purities of 98.1 and 99.0%, respectively. Single-crystal structures incorporating theoretical calculation reveal that the high selectivity originates from the higher thermostability of 1-bromoalkane-loaded structures compared to its corresponding isomer-loaded structures, which could be further attributed to the perfect size/shape match between BrP[5]L and 1-bromoalkanes. Moreover, control experiments using its counterpart macrocycle of traditional pillararene demonstrate that BrP[5]L has better adsorptive selectivity, benefiting from the intrinsic free-rotation phenylene subunit on its backbone.