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With the expansion of the application field of robots and the complexity of the work environment and tasks, ordinary robots and various simple end-holding devices that cooperate with them are far from being able to meet the requirements of various dexterity and fine operation tasks. Immersion means that the process of painting is virtual immersion; the expression requirement for painting must be immersive. This research mainly discusses the posture control algorithm and simulation of dexterous hand in virtual reality painting. The research combines the related theoretical basis of the dexterous hand posture control algorithm with VR painting, and explores the immersive experience characteristics brought by VR immersive painting. This research will focus on the three aspects of the action state pattern recognition based on the surface electromyogram (EMG) signal, the algorithm of the dexterous hand virtual control system, and the simulation of the bionic dexterous hand EMG control system. The collection and processing of the surface EMG signal of the forearm were completed. The experiment verified the effectiveness and accuracy of the surface EMG signal feature extraction, feature dimensionality reduction, and classification algorithm, and realized the pattern recognition of eight action states. Using musculoskeletal simulation software and a finite state machine control model, an intelligent bionic dexterous hand virtual control system was established, which realized offline gesture recognition and performance evaluation of the virtual control system. In the environment of large time delay, many painting experiments were carried out, the tasks were successfully completed, and the average completion time was about 4 min. At this stage, most of the finger structures of dexterous hands are in series, and the accumulated error is large, which greatly affects the accuracy of dexterous hands. VR painting is an innovative form of painting with potential space in the future. The results of this research and exploration can reflect the potential possibilities of future painting creation forms.