We investigate the structures and properties of Ge4C-/0 and Ge4CH-/0 clusters using anion photoelectron spectroscopy and theoretical calculations. Our calculations show that the first two low-lying isomers coexist in the experiments of Ge4C- and Ge4CH-. The first two low-lying isomers of Ge4C- have trigonal bipyramidal structures with the C atom on the equatorial plane and the top vertex, respectively. It is found that the first two low-lying isomers of Ge4CH- can be obtained by adding an H atom to the top and equatorial C atoms of Ge4C-, respectively. The AdNDP analyses reveal that the C atom in Ge4C forms one 4c-2e σ bond, two 4c-2e π bonds, and one 5c-2e σ bond with Ge atoms. The C atom in Ge4C interacts with an H- forming a C-H σ bond in Ge4CH-. AIMD simulation results indicate high dynamic stabilities of Ge4C and Ge4CH- at 300 and 500 K. Our results show that the structures and chemical bonding of Ge4B- and Ge4N+ are similar to those of Ge4C, while those of Ge4BH2- and Ge4NH resemble those of Ge4CH-.