Pillar[5]arene-based multilayer films are constructed by layer-by-layer assembly with consecutive adsorption of cationic and anionic pillar[5]arenes. The films have active pores that allow shape-selective uptake of dinitrobenzene isomers: the film adsorbs para-dinitrobenzene, but not ortho- and meta-dinitrobenzene. The ability of the film to adsorb para-dinitrobenzene is result of the surface electrostatic potential: para-dinitrobenzene adsorbs on films with a positive surface, but not on films with a negative surface. The adsorbed amount of para-dinitrobenzene exponentially increases with increasing number of deposited layers.