Although plasticizing materials by modification with small‐molecular chemicals has been extensively utilized in the industrial community, processing poly(vinyl alcohol) (PVA) at high concentrations (CPVA) or with a high degree of polymerization (DP) remains challenging. Optimization the plasticizing conditions is one means of addressing this issue. In this study, two types of frequently used plasticizers, glycerol (GLY) and diethanolamine (DEA), are chosen to plasticize PVA resin with a DP of 2400. Both PVA/plasticizer films possess excellent optical transmittance and mechanical ductility, whereas the films blended with DEA exhibit higher strength than the PVA/GLY films. The viscosity variation in the temperature (Top)–CPVA space is monitored by real‐time viscous flow testing, demonstrating that DEA is more effective for reducing the viscosity of PVA, which should improve the processability, facilitating film‐forming from concentrated solutions. Furthermore, density functional theory calculations and molecular dynamics simulations illustrate that the PVA/DEA system has a lower binding energy, longer hydrogen bond length, and higher isotropic diffusion coefficient, indicating a stable hydrogen bond network and homogenous dispersion of the plasticizer, leading to good solution fluidity and mechanical performance. This study is significant for guiding the design and manufacture of optically transparent, high‐performance PVA films as polarizer precursor.