The influence of degassing time and temperature on low-pressure gas adsorption (LPGA) behavior of shales was examined in this study. Two organic-rich shales of contrasting maturity, reactivity and organic matter type, were crushed to <1 mm and <212 μm grain-sizes and degassed at 110, 200, and 300 °C for 3 and 12 h, respectively. Our results indicate that degassing duration has a minimal influence on pore-character interpretations from LPGA experiments, while the degassing temperature shows a strong influence on the pore attributes. For both shales, reliable porosity estimates were obtained when the samples were degassed at 110 °C. When the degassing temperature was increased to 200 and further to 300 °C, distinct changes in adsorption isotherms and other pore structural features were observed. For the mesoporous low-mature shale (collected from a lignite mine) when the degassing temperature was kept at 200 °C, a macroporous character was induced with a manifold increase in pore diameter. Results from thermogravimetry and Rock-Eval indicate abundance of reactive kerogen, which undergoes alteration when degassed at higher temperatures. When the degassing temperature was kept at 300 °C, the organic matter underwent further alteration and showed an isotherm similar to the shales degassed at 110 °C. Similarly, for the oil-window mature shale sample, a transition towards macroporous structure was observed when the sample was degassed at 200 and 300 °C, compared to a mesoporous structure observed when degassed at 110 °C. The results from fractal dimensions also support the above inferences, indicating the presence of simpler structures at higher degassing temperatures. Reduction in pore volume (110–200 °C) and its further rise (200–300 °C) are also evident in the micropore domain, more distinctly in the oil window mature shale. Our results strongly indicate that degassing temperature should be kept at around 110 °C for reliable shale pore character estimation.