To provide new insight into the field of urea‐formaldehyde (UF) adhesives science, in this work, for the first time, UF resin was modified with hydrochar of spent mushroom substrate (HCUF) and chitosan (CHUF) to investigate the effect of these bio‐fillers on the hydrolytic and thermal stability of in situ prepared UF resins. The characterization of the modified UF biocomposites was performed using X‐ray diffraction analysis (XRD), Fourier transforms infrared spectroscopy (FTIR), non‐isothermal thermogravimetric analysis (TG), differential thermal gravimetry (DTG), and differential thermal analysis (DTA). Scanning electron micrographs (SEM) of the CHUF and HCUF biocomposites show a spherical structure that differs from each other because the surface of the CHUF biocomposite has pronounced pores that form a network structure. With its hydroxyl and amino groups, chitosan bonding to UF resin through hydrogen bonds, which is confirmed by FTIR analysis. The content of free FA in CHUF biocomposite is 0.06%, while that of HCUF is higher and amounts to 0.48%. The content of released FA in both modified UF biocomposites was similar (2.5% and 2.8% for CHUF and HCUF, respectively). The hydrolytic stability of CHUF is slightly higher compared to the HCUF biocomposite. Thermal analysis shows that the CHUF is thermally more stable because it starts to decompose at a slightly higher temperature than the HCUF biocomposite.