Urea formaldehyde (UF) is the most widely used resin in the wood composite board industry. UF has formaldehyde emission, which is harmful to the environment and human health. In this paper, hydroxyapatite (HAP) was surface modified by silane coupling agent (HAP-KH). And hydroxyapatite/urea formaldehyde resin (HAP-UF) was prepared by adding different amounts of HAP-KH. The optimal amount of HAP-KH was determined by wet shear strength and formaldehyde release. The degradation performance and degradation kinetics of the resin were also studied. The results show that the addition of HAP-KH can improve the wet shear strength of plywood and reduce the release of formaldehyde. The optimal content of HAP-KH was 3%, and the formaldehyde emission of plywood reached the lowest level of 0.35 mg L−1, 52.32% lower than that of the control resin. The wet shear strength was 1.14 MPa, 14.4% higher than that of the control resin. HAP-KH had no significant effect on the thermal stability of UF resins. However, HAP-KH has a significant effect on the thermal degradation mechanism of UF resins. The most likely kinetics mechanism models for UF and HAP-UF are G(a) = [−ln(1−α)]2 and G(a) = [−ln(1−α)]3, respectively.