Investigating shale pore characteristics has deepened our understanding of shale reservoir, while that of postmature-overmature shales is yet to be revealed, which is especially critical for shale gas evaluation in southern China. Ten Middle-Upper Devonian organic-rich shale samples were collected from well GY-1 in the Guizhong Depression, and the paleoenvironment, geochemistry, and pore system were analyzed with a series of experiments, including trace element analysis, X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), low-pressure N2 adsorption, and source rock geochemistry. Results show that the Middle-Upper Devonian shales in the Guizhong Depression are organic-rich mudstones with TOC ranging from 0.14% to 6.21%, which is highest in the Nabiao Formation (
D
2
n
) and Lower Luofu Formation (
D
2
l
) that were deposited in the anoxic and weak hydrodynamic deep-water shelf. They are thermally postmature to overmature with equivalent vitrinite reflectance (
EqV
R
o
) of 3.40%~3.76% and type I kerogen. The lithofacies in
D
2
n
and
D
2
l
are primarily siliceous/argillaceous mixed shale as well as a few siliceous argillaceous shales and argillaceous siliceous shales as well. Organic matter- (OM-) hosted pores within bitumen are primary storage volume, rather than inorganic pores (interparticle and intraparticle) which are rare. The total helium porosity of samples varies between 1.20% and 4.49%, while total surface area and pore volume are 2.39-14.22 m2/g and 0.0036-0.0171 ml/g, respectively. Porosity, pore surface area, and pore volume are in accordance with increasing TOC,
R
o
, and siliceous mineral contents. Considerable OM-macropores are found in shales with
R
o
>
3.6
%
in our study which demonstrates that the porosity at postmature to overmature stage (
R
o
=
3.5
−
4.0
%
) does not change fundamentally. The high level of maturity is not considered the main controlling factor that affects shale gas content, and more attention should be paid to preservation conditions in this area.