A new emissive molecular probe derived from 1,7-bis(2′-formylphenyl)-1,4,7-trioxaheptane and 2-hydroxy-1-naphthaldehyde has been synthesized by a Schiff-base condensation method. Its sensor capability towards cations such as Cu2+, Zn2+, Cd2+ and Hg2+, and anions such as halides (F−, Cl−, Br− and I−) and CN− was explored in DMSO solution. The geometry was optimized using density functional theory (DFT). The probe showed remarkable selectivity for Cu2+ and interaction with the more basic anions CN− and F−.