Benzo[g]coumarins, which consist of coumarins fused with other aromatic units in the linear shape, have recently emerged as an interesting fluorophore in the bioimaging research. The pi-extended skeleton with the presence of electron-donating and electron-withdrawing substituents from the parent coumarins changes the basic photophysical parameters such as absorption and fluorescence emission significantly. Most of the benzo[g]coumarin analogues show red/far-red fluorescence emission with high two-photon absorbing property that can be applicable for the two-photon microscopy (TPM) imaging. In this review, we summarized the recently developed benzo[g]coumarin analogues including photophysical properties, synthesis, and applications for molecular probes that can sense biologically important species such as metal ions, cell organs, reactive species, and disease biomarkers.