During screening studies to find new glycopeptide antibiotics, we elucidated the structure of orienticins which have excellent antibacterial activity against methicillin-resistant Staphylococcus aureus equivalent to vancomycin. We isolated new vancomycin-type antibiotics, chloroorienticins (including A, B, C, D, and E), from the fermentation broth of Amycolatopsis orientalis (Nocardia orientalis) PA-45052. In this communication paper, we report the isolation of chloroorienticins and their structures. The chloroorienticin complex was separated by MCI gel CHP20P (Mitsubishi Chemical Industries Limited) column and Packed column RQ-2 (C18, Fuji gel) chromatography. The structures of these molecules were elucidated by ¹H, ¹³C NMR and mass spectroscopies and confirmed by chemical transformations or degradations. Chloroorienticin A is very similar to orienticin A but has Cl substitutions at positions A-3 and C-5 (like vancomycin), which was confirmed by selective hydrogenolysis to orienticin A and hydrolysis to the aglycone of vancomycin and identification of sugar parts (D-glucose and L-4-epi-vancosamine). Chloroorienticin B, one of the major components, lacks one of the 4-epi-vancosamine units from chloroorienticin A and was identified from the products of partial hydrolysis of chloroorienticin A. Chloroorienticin C, a major component, lacks D-glucose from chloroorienticin B. Physico-chemical properties such as specific rotation ([α]ₙ), elemental analysis, and molecular formulas of chloroorienticins A-E are also described.