The present article describes the synthesis of Schiff base-acetylene functionalized organosilatranes (6a–6e) and their characterization by 1H and 13C NMR spectroscopy and ESI-QTOF mass spectrometry. The UV–visible study of the organosilatrane 6a unveiled their high selectivity towards the recognition of Zn2+ and Co2+ ions without exhibiting any significant interference from other competitive metal ions. The calculated value of association constant with 6a for Zn2+ and Co2+ ions was 0.11 × 106 M−1 and 0.24 × 106 M−1 and the limit of detection was 0.28 × 10−6 M and 0.82 × 10−6 M respectively. Furthermore, DFT calculations were performed to get an insight into the interacting behaviour of sensor 6a towards Zn2+ and Co2+ ions. © 2021