The valorization of lignocellulosic biomass by-products holds significant economic and ecological potential, considering their global overproduction. This paper introduces the fabrication of a novel wheat-straw-based hydrogel and a new microcellulose-based hydrogel through 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) oxidation. In this study, Fourier transform infrared (FTIR) analysis was employed for the detection of carboxyl groups, neutralization titration was conducted using a conductivity meter, viscosity analysis was performed using a rheometer, and transmittance analysis was carried out using a spectrophotometer. Two novel hydrogels based on TEMPO oxidation have been developed. Among them, the bio-based hydrogel derived from oxidized wheat straw exhibited exceptional printability and injectability. We found that the oxidation degree of microcellulose reached 56–69%, and the oxidation degree of wheat straw reached 56–63%. The cross-linking of 4% oxidized wheat straw and calcium chloride was completed in 400 seconds, and the viscosity exceeded 100,000 Pa·s. In summary, we have successfully created low-cost hydrogels through the modification of wheat straw and microcellulose, transforming lignocellulosic biomass by-products into a sustainable source of polymers. This paper verifies the future applicability of biomass materials in 3D printing.