Two fluorescent sensors with the receptor semicarbazide respectively at 7- (CAA) and 3-position (CAB) of coumarin were designed and synthesized. CAA exhibits fluorescence turn-on response to Cu2+ by triggering the intramolecular charge transfer (ICT) process via Cu2+-catalyzed hydrolysis, and can detect formaldehyde (FA) at different channel by inhibiting the photo-induced electron transfer (PET). However, CAB displays quite different responses: the photophysical properties hardly changed in the presence of FA; while a three-stage fluorescence response of fast quenching, steady increasing and slowly decreasing was found upon addition of Cu2+. The high selectivity enabled CAA a good candidate for quantification of Cu2+ and formaldehyde as well as bioimaging Cu2+ in living cells. Good linear relationships between the fluorescence intensity and analyte concentration were observed in the range of 0.1–30 μM for Cu2+ and 1.0–50 μM for FA, and their detection limits (LOD) were calculated to be 0.43 μM and 1.92 μM (3δ/k), respectively.