Blends of multicyclic and linear polymers under biaxial elongational flow were analyzed using coarse-grained molecular dynamics simulations. The multicyclic/linear blends displayed overshoot in the normal stress difference at the start-up of the biaxial elongational flow. This overshoot was steeper for multicyclic/linear blends than for our previously reported monocyclic/linear blends [Murashima, T.; Hagita, K.; Kawakatsu, T. Macromolecules2021,54, 7210-7225]. Investigation of the origin of the overshoot in the multicyclic/linear blends revealed a different mechanism than that previously observed in our monocyclic/linear blends. Specifically, a "topological transition" mechanism comprising a morphological change from the open- to closed-ring state was observed in the multicyclic chains, but not in the monocyclic chains. This topological transition drastically changes the stress of the rings. Although the topological transition was also observed in asymmetric-multicyclic/linear blends, no stress overshoot appeared, owing to the asymmetry in the multicyclic chains. Therefore, we hypothesized that the structural symmetry in multicyclic chains is indispensable for the overshoot behavior to occur. We determined that the topological transition in multicyclic chains with structural symmetry induces the stress-overshoot behavior in multicyclic/linear blends under biaxial elongational flow.