We study exotic orbits in the photoassociation process by considering both the vibrational and rotational motions in a classical model. In the presence of rotational motion, the exotic orbits possess regular bound segments even when the total energy exceeds the threshold energy of the interaction potential. Such features of the exotic orbits are interpreted by introducing an effective potential. We employ Lagrangian descriptors and escape time to characterize the phase-space structure and show that exotic orbits are distributed around the stable region in the short-range phase space. We further calculate the photoassociation probability. Our work provides new insights into the dynamical mechanisms of photoassociation processes.