The biceps and triceps alternatively act as agonists and antagonists to realize upper limb movement. Pneumatic artificial muscle (PAM), which is inflated and deflated with compressed air instead of water, has similar characteristics to those of human muscle. The challenge is whether an exoskeleton actuated by PAM can help biceps lift the upper limb. Accordingly, the principal aim of this research is to guarantee precise signal collection and control process and adopt the synergy control of PAM and upper limb. In this system, the biceps and triceps provide the main signals in synergy control, electrodes are pasted outside of biceps and triceps to sample their electromyogram signal (EMGs), and the mechanical structure and control system of the pneumatic exoskeleton are proposed. The relationship between duty-ratio-controlled variables and PAM contraction speed is given by experimental analysis, and the maximum duty ratio of controlled variables of input is set to 80. The feature analysis of EMGs can be various including envelope, moving average, and moving root mean square (RMS). The envelope is taken to extract muscle contraction information through upper limb muscles in a static contraction experiment. Then, the processes of biceps and triceps EMGs feature changes including rapid swing, slow swing, and discontinuous swing under various loads are analyzed during upper limb muscle dynamic contraction. The duty-ratio-controlled variables can be divided into five levels, which correspond to exertion rating from powerless to very strong in two EMG characters. These can be reflected in a scatter diagram of duty-ratio-controlled variables and average EMG characters. A nonlinear relationship can be transferred into the continuous system by the polynomial interpolation method, solving the problem of saturation. The net duty-ratio-controlled variables are adopted to control the on-off state and pulse-width modulation (PWM) duty ratio of the high-speed on-off valve. The forearm lifting up movement is unpowered and powered with various load EMGs, and elbow discontinuous swing angle overshoot is performed to analyze the coordination effect in a synergy control experiment.