Tetrahedral semiconductors such as Si adopt a diamond-type crystal structure with low packing density arising from open cavities in the crystallographic space. By taking LiAlGe as an example, we propose a zincblende-type framework as a platform for semiconductors possessing electroactive cavities. LiAlGe adopts a half-Heusler-type crystal structure including an ordered diamond-type sublattice (zincblende-type) (AlGe) and is an indirect semiconductor with a band gap of ∼0.1 eV. The conduction band minimum (CBM) is uniquely located at the cavity space surrounded by four cations (Al4) in real space. The bond ionicity and cation (Al) p orbitals located around the Fermi energy are requisite for the CBM to float in the cavity space. DFT calculations indicate the conversion of the semiconductor to a semimetallic electride under a pressure of ∼8 GPa, which is accompanied by band gap collapse due to electron transfer from valence band maximum to the cavity space. The high-pressure electride of LiAlGe formed under a very small critical pressure is derived from the presence of inherent crystallographic cavities having deep orbital levels energetically. This finding suggests the possible utilization of electroactive cavity spaces in tetrahedral semiconductors, which are widely used in modern electronic devices.