Quartz and feldspar are usually exist in symbiosis in nature, and they are difficult to be separated effectively by conventional physical methods owing to their similarities in crystal structures and surface characteristics. Flotation is the most resultful method, and especially, flotation with hydrofluoric acid (HF) is the most efficient way. Because HF may cause serious environmental and health problems, the effective and environmentally friendly separation of quartz and feldspar remains a formidable challenge. The crystal structure, surface broken bonds, surface energy, and solid-liquid interface properties of quartz and feldspar are investigated in this paper. In particular, some types of mixed cationic/anion collectors and their interaction mechanism on the quartz and feldspar surfaces with acidic, alkaline, and neutral media in the absence of fluorine are discussed, and the grade and scheme of quartz and feldspar for the practical application are illustrated. This review proposes concrete research approaches and provides perspectives for the advanced processing of quartz and feldspar in an environmentally friendly and economical way.