For the characteristics of fast detection and good selectivity about fluorescence probe for recognition to metal ions, the synthesis of probes 6-(3,5-dimethyl phenoxy)-5-amine-2-phenylbenzothiazole (L4) and 6-(3,5-dimethyl phenoxy)-5-benzamide-2-benzothiazole (L5) was designed. The molecule structures of L4 and L5 were confirmed by spectroscopic characterization and single crystal diffraction analysis. The effects of probes L4 and L5 on recognizing to trivalent metal ions Al³⁺, Cr³⁺, Fe³⁺and divalent metal ion Cu²⁺ in the solution were investigated in detail by UV-Vis and fluorescence. The results showed when the molecule of probe L5 was formed by the benzoyl recognizing group bonding with the amine group of probe L4, the fluorescence of probe L4 was quenched, and the turn-on fluorescent probe L4 and the turn-off fluorescent probe L5 were simultaneously obtained. The UV-Vis results show that probe L4 could selectively identify to Al³⁺, Fe³⁺, Cu²⁺ in the organic solution and highly selectively identify to Cu²⁺ in the aqueous acetonitrile solution. A test paper of probe L4 could effectively identify to Cu²⁺ in pure water by the naked eye detection under UV irradiation. Probe L5 could selectively identify to Al³⁺ and Fe³⁺ in the organic solution. The fluorescence results show the fluorescence of probe L4 was quenched while probe L4 with Fe³⁺, Al³⁺, Cu²⁺ were coexisted in the organic solution, respectively. Probe L4 could highly selectively recognize to Cu²⁺ in the aqueous acetonitrile solution. The fluorescence intensity of probe L5 was successively increased while probe L5 with Cr³⁺, Fe³⁺, Al³⁺ and Cu²⁺ were coexisted in the organic solution, respectively. According to the L4 solution concentration to the absorption intensity was plotted, and the detection limit of probe L4 to Cu²⁺ is 4.51×10^-6 and the complex constant is 1.12×10³ M^-1. The detection limits of probe L5 to Al³⁺, Cr³⁺, Fe³⁺, Cu²⁺ are 2.85×10^-6, 4.79×10^-6, 5.95×10^-6 and 3.23×10^-6 mol·L^-1, respectively, and the complex constants of probe L5 to Al³⁺, Cr³⁺, Fe³⁺, Cu²⁺ are 2.17×10³, 2.06×10³, 3.92×10³, 4.43×10³ M^-1, respectively. It was inferred that 1:1 complex was formed by the linkage of probes with metal ions on the basis of the results of fluorescence titrations. The results of anti-interference to other metal ions display the identification to specific metal ions by probes is not affected by other interference metal ions. ¹H NMR results show the amine group and dimethyl phenoxy group of probe L4 and the benzamide group and dimethyl phenoxy group of probe L5 play an important role in the identification of metal ions. Probe L4 has a positive application prospect on identifying to copper ions.