The development of fluorescence turn‐on probes for selectively sensing toxic gases and visualization identification of fingerprints is significantly important for society security and human health. Here, Zr is used as the metal center and 1,3,6,8‐tetra (4‐carboxylphenyl) pyrene (TBAPy) and tetrakis(4‐carboxyphenyl)porphyrin (TCPP) as double linkers to synthesize a novel Zr(TBAPy)5(TCPP) material. Results indicate that Zr(TBAPy)5(TCPP) can be used as a fluorescence turn‐on probe for highly selective and sensitive detection of H2S gas and its derivatives S2− in aqueous solutions with an extremely low concentration (≈1 ppb) and fast response time (<10 s). Moreover, by tailoring the particle size of samples, it is found that Zr(TBAPy)5(TCPP) can efficiently achieve the visualization identification of fingerprints due to the fluorescence turn‐on effect. All the results indicate that the Zr(TBAPy)5(TCPP) is a promising multifunctional fluorescence turn‐on probe.