In this work, a novel low dielectric constant (low-k) pore sealing approach was engineered by depositing firstly a sub-2 nm SAMs and then a 3 nm TiN barrier film. The low-k film was pretreated by plasma to introduce hydroxyl groups onto the surface, followed by SAMs deposition. Then a TiN film was deposited from tetrakis(dimethylamino)titanium (TDMAT) via ALD as a dielectric barrier. Penetration of Ti atoms into low-k was measured and used to evaluate the sealing ability of SAMs. For the samples covered with SAMs, around 90% reduction of Ti atoms penetration was achieved. The pore radius was reduced to below 0.5 nm after the barrier deposition. The ∆k after pretreatment and after SAMs are 0.1 and 0.16, respectively.