Water quality, particularly hardness, plays an important role in affecting the floatability of minerals as it interferes with the chemical/electro-chemical characteristics of mineral surfaces and their interactions with flotation reagents. It could become unpredictable when water sources characterized by different calcium or magnesium ion distributions were involved. This study aimed to identify the role of Ca²⁺/Mg²⁺ ions in the recycled water on the cationic reverse flotation selectivity of iron oxides through a series of bench/micro flotation tests, zeta potential, powder contact angle, and Fourier Transform Infrared (FTIR), etc. The results pointed out that the use of recycled tailing water deteriorates the flotation selectivity and dilutes the concentrates. This can be largely attributed to the presence of Ca²⁺ ions at higher concentrations as they induce a drop in the Fe recovery and an increase in SiO2 content while an increase in the content of Mg²⁺ ions seems to have little effect on the quality of concentrate. As evidenced by the data from micro-flotation, powder contact angle, zeta potentials, and FTIR, a hydrophilic colloidal layer formed by Ca-based hydrolyzed compounds, such as Ca(OH)⁺ or, CaCO_3(s), etc., on quartz could change its zeta potentials and disturb its interactions with a cationic collector. They also play a role in weakening the flocculation of starch on hematite probably by pre-locking the acidic groups on the starch remnants and contracting their configurations, thus preventing their adsorption on mineral surfaces. However, magnesium ions seem to be beneficial to in strengthening the flocculation of starch on hematite as magnesium-based species could act as adsorption bridges of between starch and mineral surfaces.