Continuous decrease of the feature size of transistors in modern integrated circuits (ICs) constrains thickness of auxiliary dielectric layers in interconnects because of their relatively high dielectric constant, which reduces the efficiency of low-k material integration. Dielectric materials used today as barrier or etch-stop layers are usually SiN (k ∼ 7.0) and SiCN (k ∼ 4.8), which k-value significantly exceeds that of recent ultra low-k materials (k < 2.2). In our work we have investigated thin films of rigid-chain polyimide (PI) with a k-value of about 3.2-3.3. This film was deposited using a Langmuir-Blodgett (LB) technique and can be as thin as several monolayers. The intermolecular interaction of densely packed precursor macromolecules within a monolayer formed at the water-air interface makes it possible to avoid penetration of precursor material inside the pores. The latter peculiarity of the deposition process results in a pore sealing effect using a 4 nm PI film.