This paper studies the problem of optimizing the kinematic structure of an eight degree-of-freedom upper-limb rehabilitation exoskeleton. The objective of optimization is achieving minimum volume and maximum dexterity in the workspace of daily activities specified by a set of upper-arm configurations. To formulate the problem, a new index is proposed for effective characterization of kinematic dexterity for wearable robots. Additionally, a set of constraints are defined to ensure that the optimal design can cover the desired workspace of the exoskeleton, while singular configurations and physical interferences are avoided. The formulated multi-objective optimization problem is solved using an evolutionary algorithm (Non-dominated Sorting Genetic Algorithm II) and the weighted sum approach. Among the resulted optimal points, the point with least sensitivity with respect to the variations of design variables is chosen as the final design.