Developing biobased thermoplastic polyurethane (TPU) from renewable biomass resources is becoming urgent due to resource scarcity and environmental protection requirements. Herein, a chain extender diol (VAN-OH) containing dynamic imine bonds was synthesized using renewable biomass resource vanillin (VAN), then combined with 1,4-butanediol (BDO) in various proportions, and reacted with poly(caprolactone diol) and 4,4 '-diphenylmethane diisocyanate to synthesize degradable biobased TPU (BTPUs) with excellent performance. Fourier transform infrared, 1H NMR, X-ray diffraction, DMA, thermogravimetric analysis, molecular weight, chemical degradation, and mechanical tests systematically investigated the relationships between the polymer chain structure and the performance of BTPUs. The experimental results demonstrated that the high regularity and strong polar bonds (imine and ether) of VAN-OH enhanced the interactions between macromolecular chains and improved the hydrogen bonding combination, crystallinity, and phase separation of BTPUs, thereby exerting significant contributions to their thermomechanical and degradable properties. BVTPU1 with a mole ratio of BDO/VAN-OH = 7.5:2.5 exhibited the best mechanical performance, degradation time was 37.5% shorter, and initial pyrolysis temperature increased by 13.8% compared to BTPU0 without VAN-OH. In addition, BTPUs have shown some biodegradability and environmental friendliness in soil burial experiments under natural conditions.