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Wood–plastic composites (WPCs) are a type of environmentally friendly materials widely used in daily life. This paper selected low-value biomass, corn stalk (CS), as the lignocellulosic resource for polyvinyl chloride (PVC)-based WPCs. To depict the relationship between lignocellulosic composition (cellulose, hemicellulose, and lignin) and mechanical performance of WPCs, pretreatments have been optimized to selective removal of lignin using an alkaline-EtOH stewing process and selective removal of hemicellulose using an acid stewing process. The αC sample, in which both lignin and hemicellulose were removed, shows the highest degree of crystallinity (72.60%) as estimated from X-ray diffraction analysis results and fibrous morphology with the highest aspect ratio as seen in scanning electron microscopy images. Compared with PVC/CS, PVC/αC gives a substantial increase in tensile strength and modulus by 37.21 and 21.66% and flexural strength and modulus by 29.98 and 34.88%, respectively. These improvements lie in the reinforcing effect of a fibrous structure and the improved interfacial compatibility as proven by scanning electron microscopy and dynamic mechanical analyzer results. Considering the extracted lignin and hemicellulose can be further developed to valuable biochemicals, the pretreatment to CS adds value to both WPC materials and biorefinery products.

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