Shale gas exploitation has been the game-changer in energy development of the past decade. However, the existing methods of estimating gas in place in deep formations suffer from large uncertainties. Here, we demonstrate, by using novel high-pressure experimental techniques, that the gas in place within deep shale gas reservoirs can be up to five times higher than that estimated by implementing industry standard approaches. We show that the error between our laboratory approach and the standard desorption test is higher for gases with heavier compositions, which are of strongest commercial interests. The proposed instrumentation is reliable for deep formations and, provides quick assessment of the potential for the gas in place, which could be useful for assessing hydrocarbon reservoirs, and the potential for geological carbon sequestration of a given formation.