Hydrogen bonds (H-bonds) in poly(vinyl alcohol) (PVA) play a crucial role in macroscopic mechanical properties, particularly for stretchability. However, there is still some ambiguity about the quantitative dependence of H-bond interactions on the mechanical performance, mainly attributed to the difficulty in the discrimination of various H-bond types. Herein, small molecular chemicals as plasticizers were incorporated into the PVA matrix to tailor the H-bonding interactions. By altering the PVA molecular weight, plasticizer type and loading, both the stretchability and H-bond content were regulated on a large scale. By a combination of DMA, IR spectroscopy, MD simulation and solid-state 13C-NMR, every sort of H-bond in PVA was assigned, and their relative fractions were ascertained quantitatively. After correlating the elongation ratio with the relative fraction of the different types of H-bonding interaction, it was found that all the pairs of elongation vs. intermolecular H-bond content derived from different series of PVA/plasticizer films could be plotted into a master curve and exhibited good linearity, indicating that intermolecular H-bonds dominate the mechanical stretchability in PVA films. Our efforts contribute towards an in-depth understanding of performance optimization induced by H-bond manipulation from empirical, phenomenological aspects to intrinsic, numerical insights.