We report on the synthesis, crystallographic and transport properties of the Zintl phase BaGe₅, which crystallizes in a new clathrate-type structure. This compound was synthesized by the decomposition of the type-I clathrate Ba₈Ge₄₃□₃ subjected to annealing treatment at 623, 673 and 793 K. Electrical resistivity, thermopower and thermal conductivity measurements were performed in the temperature range 2 – 773 K and complemented by magnetization, specific heat and Hall experiments below room temperature. Additional information on the chemical bonding and electronic band structure in BaGe₅ was obtained through the electron localizability indicator (ELI) and the total density of states, all calculated within the all-electron full-potential local orbital method (FLPO). In agreement with the chemical bonding and electronic band structure calculations, electrical resistivity and specific heat data show that BaGe₅ is a semiconductor. The complex crystal structure of BaGe₅ contributes to the low thermal conductivity which displays a conventional crystalline-like behavior. Further measurements were carried out on samples annealed at 623, 673 and 793 K for four up to 30 days to probe possible variations of the crystal structure and electronic properties as a function of the annealing temperature and time. Even though the annealing temperature does not alter the semiconducting nature of this material, differences in the absolute values of the transport properties were unveiled in samples annealed for short-time periods. These differences are significantly reduced in samples which underwent long-time annealing treatment even though the measured curves do not merge completely.