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This study measured the infrared spectra of secondary minerals in the oxidation zones of three types of copper ores: dioptase, malachite, and azurite, and assigned the peak positions of OH stretching vibrations and the origins of OH combination vibrations. Dioptase contains three types of water molecules with different orientations within its ring channels, which exhibit six kinds of OH stretching vibrations in the 3000–3600 cm⁻¹ range; the bond length range is 2.652 to 2.887 Å. Among them, the 3443 cm⁻¹ band shows strong near-infrared activity and combines with Si–O vibrations or OH bending vibrations in the structure, resulting in five combination vibration peaks in the 4000–5000 cm⁻¹ range. Malachite contains two inequivalent hydroxyls in its structure, leading to two OH stretching vibrations in the high-frequency region located at 3314 and 3402 cm⁻¹, respectively. Azurite contains only one type of hydroxyl, and thus only one characteristic OH stretching vibration is present at 3424 cm⁻¹. The OH stretching vibrations of malachite and azurite mainly combine with [CO₃]²⁻ vibrations or OH bending vibrations, leading to six and five combination peaks in the OH combination vibration region, respectively. By analyzing the combination of peak positions at 4341 cm⁻¹ in the near-infrared spectrum, the merged OH bending vibration at 921 cm⁻¹ in azurite was discovered. Spectroscopic research on secondary minerals can better provide a basis for ore exploration and geological remote sensing. Full article