Thermal and photoinduced processes accompanying complexation of photochromic spiropyrans (SPP) with Zn ions in acetone solution were characterized by means of UV-vis and X-ray absorption spectroscopies in operando regime. SPP ligands are usually transparent at lambda > 350 nm, but after mixing with Zn ions, they produce a stable colored (epsilon = 32 000-38 000 M-1 cm(-1)) complex with maximum absorption at 525 nm, which makes them a powerful tool for monitoring metal-ion concentration in solution. The complex revealed fluorescence and photochromic behavior under static irradiation with visible light with constant photoreaction quantum yield across its characteristic absorption band. Zn K-edge X-ray absorption spectra show prominent changes in Zn local atomic structure between free Zn ions and Zn complex. The pump-flow-probe scheme was adapted to measure operando changes in Zn coordination upon light irradiation. Within experimental time resolution, we have determined that 20 mu s after light irradiation, Zn ion is released out of the complex. This is the first example of the direct spectroscopic probe of the Zn photorelease from the spiropyran complex.