Upper limb exoskeletons have drawn significant attention in neurorehabilitation because of the anthropomorphic mechanical structure analogous to human anatomy. Whereas, the training movements are typically unorganized because most exoskeletons ignore the natural movement characteristic of human upper limbs, particularly inter-joint postural synergy. This paper introduces a newly developed exoskeleton (Armule) for upper limb rehabilitation with a postural synergy design concept, which can reproduce activities of daily living (ADL) motion with the characteristics of human natural movements. The semi-transparent active control strategy with the interactive force guidance and visual feedback ensured the active participation of users. Eight participants with hemiplegia due to a first-ever, unilateral stroke were recruited and included. They participated in exoskeleton therapy sessions for 4 weeks, with passive/active training under trajectories and postures with the characteristics of human natural movements. The primary outcome was the Fugl-Meyer Assessment for Upper Extremities (FMA-UE). The secondary outcomes were the Action Research Arm Test(ARAT), modified Barthel Index (mBI), and metric measured with the exoskeleton After the 4-weeks intervention, all subjects showed significant improvements in the following clinical measures: the FMA-UE (difference, 11.50 points, p = 0.002), the ARAT (difference, 7.75 points p <0.001), and the mBI (difference, 17.50 points, p = 0.003) score. Besides, all subjects showed significant improvements in kinematic and interaction force metrics measured with the exoskeleton. These preliminary results demonstrate that the Armule exoskeleton could improve individuals' motor control and ADL function after stroke, which might be associated with kinematic and interaction force optimization and postural synergy modification during functional tasks.