In this study, the adsorption behavior of CaAl-Cl layered double hydroxide (CaAl-Cl-LDH) with a controlled pH value (pH = 6) on Co(II) ions ([Co] = 8 mM) is investigated. The comprehensively accepted mechanism of cobalt adsorption on LDH is considered to be co-precipitation, and the final adsorbed products are normally crystalline Co-LDH. One unanticipated finding is that crystalline/amorphous blends are found in the X-ray diffraction (XRD) pattern of Co-adsorbed LDH. To shed light on the adsorption products and the mechanisms in the adsorption process of Co(II) in an aqueous solution by CaAl-Cl-LDH, a series of testing methods including Fourier-transform infrared spectroscopy (FT-IR), Scanning electron microscope (SEM), High-resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS), and inductively coupled plasma (ICP) are applied to clarify the interaction between cobalt and CaAl-Cl-LDH. According to the comprehensive analysis, the formation of the crystalline/amorphous blends corresponds to two adsorption mechanisms. The crystalline phases are identified as Co₆Al₂CO₃(OH)₁₆·4H₂O, which is attributed to the co-precipitation process occurring in the interaction between Co(II) and CaAl-Cl-LDH. The formation of the amorphous phases is due to surface complexation on amorphous Al(OH)₃ hydrolyzed from CaAl-Cl-LDH.