Silyl anions are crucial building blocks in silicon chemistry and are frequently used in organosilicon chemistry. These so-called silanides are negatively charged three-coordinate species, isoelectronic to carbanions. In this contribution, we synthesized already literature known and unknown anionic silicon species. Here we focused on silyl substituted silyl anions with different substituted silicon atoms like hydrogen, methyl, and methoxy groups. Furthermore, we investigated these species with liquid injection field desorption ionization mass spectrometry.