Organic-matter pores are considered to be the dominant contributor to total porosity in many shale reservoirs, and consequently much attention has been paid to investigate the factors influencing their generation, especially thermal maturity. Recent studies have shown that in addition to maturation of organic matter, other diagenetic processes also play important roles in evolution of pore systems, including compaction, mineral dissolution, and quartz cementation. This study investigates the effect of thermal maturity on porosity development in the siliceous Woodford Shale by integrating multiple techniques including helium pycnometry, low pressure gas (N2) adsorption, mercury injection capillary pressure, and field emission scanning electron microscopy (SEM) analyses. We compare samples from two long cores from Woodford Shale at different levels of thermal maturity, one in the early oil window (average calculated Ro = 0.69%) and the other in the wet gas window (average calculated Ro = 1.34%).Porosity, pore size, type, and volume vary systematically with the thermal maturity increasing from early oil window to wet gas window. Porosity measured by helium pycnometry averages 4.1% for early oil window samples, and increased by approximately 50% for the wet gas window samples (average porosity =6.3%). Both pore size and pore throat size distributions display decreasing trends from early oil window to wet gas window. Petrographic examination of SEM images shows that pores developed between clay platelets dominate in the early oil window samples, and secondary organic-matter pores are the dominant pore type in wet gas window samples. Porosity shows no obvious correlation to TOC content in both oil window and gas window samples, but correlates positive to silica content, suggesting that silica content largely controls variations in porosity. Both silica nanospheres and microcrystalline quartz were observed and appear to be significant in preserving pores from compaction by forming rigid frameworks that prevent pores from collapsing. Generation of secondary organic-matter pores and preservation of primary pores by silica nanospheres account for the net porosity increase from early oil window to wet gas window.