A highly branched pillar[5]arene-based sensor containing multiple BODIPY units has been designed and synthesized (B–P[5]arene). Systematical experiments on metal ion detection of B–P[5]arene in acetonitrile/water by emission and absorption spectra indicate that this macrocycle shows high sensitivity and selectivity to both Sn (II) and Hg(II) by dual-channels. Hg (II) ions quenched to the fluorescence intensity of B–P[5]arene, while Sn (II) caused a broader spectrum without any shifting in wavelength. The detection limits of B–P[5]arene for Hg (II) and Sn (II) were found to be 1.09 × 10−6 M and 3.18 × 10−7 M, respectively. For two complex interactions, the metal ion: ligand ratio was determined as 1:2. The complex interactions between the Hg (II)&Sn(II) metal ions and B–P[5]arene are generally stable in both basic and acidic media due to strong interaction.