Basalt fiber is prone to slip and fall off in asphalt system. To improve the interfacial adhesion strength between basalt fibers (BFs) and asphalt, titanate coupling agents (TCAs) were applied to BF-reinforced asphalt. The mechanical properties of fibers with TCA concentration (6%, 8%, 10%, 12%) and infiltration time (10 min, 30 min, 60 min, 90 min) were tested by monofilament tensile strength test to obtain the best treatment conditions. The crystal phase, functional group, microstructure, and elemental changes of the TCA-treated basalt fibers were characterized by X-ray diffractometer, Fourier infrared spectroscopy (FT-IR), and X-ray energy-dispersive spectroscopy. The controlled group (untreated basalt fibers) was also prepared for comparison. Meanwhile, the adhesion work and interfacial bonding strength between asphalt and basalt fibers were compared and quantitatively assessed through pull-out tests. Additionally, the thermal stability of asphalt was evaluated using the differential scanning calorimetry test, while the surface morphology of the fractured asphalt sections was observed through scanning electron microscopy. The results show that the surface of basalt fibers was chemically modified by TCA successfully, forming octopus-inspired micro-sucker coated. Through this process, the nascent Si–O–Ti bond acts as a tie connecting the basalt and asphalt surface, which promoted the adhesive properties of BF to asphalt. Compared with the control group, the adhesion work and adhesion energy of basalt fibers-asphalt increased by 20.05% and 26.82%, respectively, and the thermal stability was improved. The experimental results show that after the treatment of the fiber surface by TCA, the interaction between the fiber and the asphalt is strengthened, and the interfacial bonding morphology is improved.