Stable, homogeneous ultrathin films of uniformly dimensioned dual-pore carbon capsules with mesoporous walls and macroscopic empty cores were fabricated using layer-by-layer methods based on electrostatic interaction between a polyelectrolyte and a surfactant coating of the carbon capsules. The resulting dual-porous carbon capsule films were investigated as a sensor substrate for vapors of different organic solvents. The carbon capsule films have much higher adsorption capacities than conventional electrolyte films and even than noncapsular mesoporous carbon films. The dual-pore carbon capsules have greater affinities for aromatic volatiles over their aliphatic counterparts, probably due to stronger pi-pi interactions. Additionally, the adsorption selectivity can be designed. Impregnation of additional recognition components into the carbon capsules permits further control over adsorption selectivity between aromatic and nonaromatic substances and between acids and bases in the prevailing atmosphere. Therefore, it is anticipated that the dual-pore carbon capsule films developed in this work will find application in sensing and separation applications because of their designable selectivity.