To study the rheological and aging properties of vegetable oil–based polyurethane (V-PU)–modified asphalt, V-PU terminated with an –NCO group was synthesized from renewable castor oil, and liquefied MDI-100LL and 10–40 wt% V-PU modified asphalts were prepared. Temperature classification, multiple stress creep recovery (MSCR), and linear amplitude scanning (LAS) tests were carried out. The results showed that the modulus, the creep recovery rate (R), and the yield stress and yield strain of the V-PU modified asphalts significantly increased in the order: 0 wt% < 10 wt% < 20 wt% < 40 wt% < 30 wt%, while the phase angle and the unrecoverable creep compliance (Jnr) changed in the opposite order, and the high temperature grade of 30 wt% V-PU modified asphalt was 4 grades higher than that of the base asphalt, which indicated that the addition of V-PU enhanced the fatigue, permanent deformation, and recovery deformation resistance. The 30 wt% sample-exhibited phase inversion had the best performance. Comprehensive FTIR, GPC, and fluorescence microscopy analyses showed that the molecular weight significantly increased and the V-PU molecules agglomerated after aging. The excess–NCO groups of V-PU prepolymer react with water in the air and the active hydrogen in the asphalt system and finally form a cross-linked three-dimensional network structure with the asphalt to improve performance. The mechanism of intramolecular cementation reaction and the aging process of V-PU-modified asphalt was creatively derived.