The invention discloses a probe reagent for concurrent selection and determination of multiple metal ions, and preparation and appliance, and belongs to the field of organic synthesis and analytical chemistry. Tri (2-aminoethyl) amine serves as a parent, wherein rhodamine B is connected to an amino chain, 2-hydroxy-1-naphthaldehyde groups are connected to other two amino chains respectively, and thus a tripod structured rhodamine-hydroxyl naphthalene derivative probe is prepared. In 1,4-dioxane/water (19/1, v/v, pH=7) solution, the probe respectively detects Cu2+, Co2+ and Fe3+ by utilizing rate absorption of different wavelengths, and the detection does not interfere with each other; in acetonitrile/water (19/1, v/v) solution, fluorescence emission of different wavelengths under different pHs is utilized, the probe respectively detects Zn2+, Al3+, Hg2+ and Cu2+, and the detection does not interfere with each other; under an ultraviolet lamp of 365 nm, Zn2+, Al3+ and Hg2+ are detected to show blue, pink and orange red fluorescence respectively, and through -Zn2+ mixture detection by the probe, Cu2+ shows blue fluorescence vanishing. The probe structure is as follows.