Elaborate chemical design is of utmost importance in order to slow down the relaxation dynamics in single-molecule magnets (SMMs) and hence improve their potential applications. Much interest was devoted to the study of distinct relaxation processes related to the different crystal fields of crystallographically independent lanthanide ions. However, the assignment of the relaxation processes to specific metal sites remains a challenging task. To address this challenge, a new asymmetric Dy₂ SMM displaying a well-separated two-step relaxation process with the anisotropic centers in fine-tuned local environments was elaborately designed. For the first time a one-to-one relationship between the metal sites and the relaxation processes was evidenced. This work sheds light on complex multiple relaxation and may direct the rational design of lanthanide SMMs with enhanced magnetic properties.