The past decades have witnessed remarkable progress in neural technologies such as functional electrical stimulation (FES) and their applications in neurorehabilitation and neuromodulation. These advances are powered by new neuroscientific understandings of the organization and compositionality of neuromuscular control illuminating how muscle groups may be activated together as discrete units known as muscle synergies. These parallel developments have promoted novel approaches to clinical rehabilitation for neurological disorders that are insurmountable to current treatments. One such breakthrough is the evolution of FES as a therapeutic tool in poststroke rehabilitation with an interventional strategy particularly inspired by the concept that muscles in humans may be purposefully coordinated through neuromotor modules represented as muscle synergies. This paper will review recent advances in multichannel FES technology, its potential applications in poststroke rehabilitation, new findings that support the neurological basis of the muscle synergies for generating natural motor tasks, and the application of the muscle-synergy concept in poststroke assessment and rehabilitation of motor impairment. Finally, we will recommend future directions of development in relation to assistive FES and synergy-driven adaptive training for poststroke rehabilitation.