Abstract Developing eco‐friendly products to replace fossil‐based ones which are difficult to degrade and pollute survival environment, is of great significance for human health and environmental protection. Here, the preparation of green polyvinyl alcohol/polylactic acid (PVA/PLA) materials has been achieved for the first time using a simple and effective strategy. Interestingly, after the composite of PVA with PLA, PLA can remarkedly enhance tensile strength, elongation at break, biocompatibility and thermostability of the PVA/PLA material. Moreover, the material is biodegradable in natural environment. At the same time, scanning electron micrograph (SEM), X‐ray diffraction (XRD) and infrared spectra (IR) techniques are employed to systematically study the effects of PVA/PLA mass ratio on the morphology, crystallinity and chemical structure of the PVA/PLA material and possible interaction between PVA and PLA. It is expected that this study can provide a new insight into the fabrication of green PVA‐based products with high performance and practical application.