In the development of ultrabarrier films for packaging electronics, the effective water vapor transmission rate is a combination of permeation through pinhole defects and the intrinsic permeation through the actual barrier film. While it is possible to measure the effective permeation rate through barriers, it is important to develop a better understanding of the contribution from defects to the overall effective barrier performance. Here, we demonstrate a method to investigate independently defect-assisted permeation and intrinsic permeation rates by observing the degradation of a calcium layer encapsulated with a hybrid barrier film, that is, prepared using atomic layer deposition (ALD) and plasma enhanced deposition (PECVD). The results are rationalized using an analytical diffusion model to calculate the permeation rate as a function of spatial position within the barrier. It was observed that a barrier film consisting of a PECVD SiN(x) layer combined with an ALD Al2O3/HfO(x) nanolaminate resulted in a defect-assisted water vapor transmission rate (WVTR) of 4.84 × 10(-5) g/m(2) day and intrinsic WVTR of 1.41 × 10(-4) g/m(2) day at 50 °C/85% RH. Due to the low defect density of the tested barrier film, the defect-assisted WVTR was found to be three times lower than the intrinsic WVTR, and an effective (or total) WVTR value was 1.89 × 10(-4) g/m(2) day. Thus, improvements of the barrier performance should focus on reducing the number of defects while also improving the intrinsic barrier performance of the hybrid layer.