Gas release from organic-rich shale rock plays a significant role in the migration and production of hydrocarbons in the shale reservoir. Despite recent progress in gas adsorption/desorption experiments and molecular simulation, information on the actual gas release process remains stagnated. Here, we demonstrate the real-time canister monitoring technique as a powerful tool to investigate the kinetics of shale gas release from freshly drilled core samples. Combined with the adsorption capacity measurement, it is found that the gas released from the core in the canister is the gas that was in the adsorbed state in the reservoir, and the free gas and a fraction of adsorbed gas were already lost during coring. Then, the reaction-based pseudo-first-order and pseudo-second-order models and the diffusion-based double-exponential (DE) model are used to interpret the kinetics of shale gas release. Instead of the coefficient of determination (R-2), the corrected Akaike information criterion technique (AIC(c)) was used to determine the best fitting model. It is found that the DE model best described the kinetics of shale gas release from the core, and the success of the DE model suggests that the shale gas release from the core is a process of first-order, two-stage, and micropore diffusion-controlled. Further, to investigate the dependence of gas release kinetics, the half-life time (t(1/2)) was calculated and correlated with the adsorption capacity, gas concentrations, and total organic matter (TOC) content. It is shown that increasing the gas adsorption capacity, gas concentrations, and TOC content could accelerate the rate of shale gas release. In addition, the potential implications and an upscaling attempt of the release kinetics in evaluating the shale gas content and production are also discussed. We found that the slow stage of gas release controls the estimated ultimate recovery (EUR) of shale gas wells, while the estimation based on the fast stage would significantly lower the EUR. Overall, by using the real-time wellsite canister monitoring technique, this study provides a unique perspective for understanding the kinetics of gas release from tight shale rock, as well as the long-term shale gas production behavior.