In this study, ball mill pretreated iron ore tailings were modified with tetraethoxysilane (TEOS) and hexadecyltrimethoxysilane (HDTMS) to obtain iron ore tailings/polysiloxane (IOT/POS) superhydrophobic powders, which were subsequently mixed with chloroprene rubber solution (CRS) to prepare durable superhydrophobic composite coatings. The effect of HDTMS amount and reaction time on the wettability of the superhydrophobic powder was investigated. The influence of the superhydrophobic powders concentration on the wettability of the composite coatings as well as the degree of damage of the superhydrophobicity of the composite coating was analyzed by using the sandpaper abrasion and tape peeling tests. Further, SEM and FTIR were used to analyze the formation mechanism of the IOT/POS superhydrophobic powders and coatings. The results showed for an HDTMS amount of 2.5 mmol and reaction time of 4 h, the contact angle of the IOT/POS powder was 157.3 ± 0.6°, whereas the slide angle was determined to be 5.9 ± 0.8°. For an IOT/POS powder content of 0.06 g/mL in CRS, the contact angle value of the superhydrophobic composite coating was 159.2 ± 0.5°, whereas the slide angle value was 5.5 ± 0.8°. The superhydrophobic composite coating still maintained the superhydrophobicity after the sandpaper abrasion and tape peeling tests, which indicated the iron ore tailings solid waste has the potential to prepare superhydrophobic coatings.