The field of wearable robotics is gaining momentum thanks to its potential application in rehabilitation engineering, assistive robotics, and power augmentation. These devices are designed to be used in direct contact with the user to aid with movement or increase the power of specific skeletal joints. The design of the so-called physical human-robot interface is critical, since it determines not only the efficacy of the robot but the kinematic compatibility of the device with the human skeleton and the degree of adaptation to different anthropometries as well. Failing to deal with these problems causes misalignments between the robot and the user joint. Axes misalignment leads to the impossibility of controlling the torque effectively transmitted to the user joint and causes undesired loading forces on articulations and soft tissues. In this paper, we propose a general analytical method for the design of exoskeletons able to assist human joints without being subjected to misalignment effects. This method is based on a kinetostatic analysis of a coupled mechanism (robot-human skeleton) and can be applied in the design of self-aligning mechanisms. The method is exemplified in the design of an assistive robotic chain for a two-degree-of-freedom (DOF) human articulation.