ESIPT-based materials (ESIPT = Excited State Intramolecular Proton Transfer) find diverse applications in optoelectronics and biomedicine owing to the peculiarities of their luminescence properties. Here, an ESIPT-capable compound 2-(3,5-dimethyl-1H-pyrazol-1-yl)-4-(2-hydroxyphenyl)pyrimidine (HL4,2,Me) featuring a short O–H⋅⋅⋅N intramolecular hydrogen bond and two N,N-sites for metal binding has been synthesized. HL4,2,Me is the first reported molecule which can act as an ESIPT molecular switch triggered by metal ion coordination without its deprotonation. Drastic changes in the HL4,2,Me conformation in the [Zn(HL4,2,Me)X2] (X = Cl, Br,I) complexes significantly alter the photoluminescence response compared to the free ligand. In the solid state, HL4,2,Me exhibits barrierless ESIPT and large Stokes-shifted yellow-orange emission due to the interplay of anti-Kasha S2 → S0 fluorescence and Kasha-like T1 → S0 phosphorescence radiative channels. The violation of Kasha’s rule for HL4,2,Me is justified by an extraordinarily large S2 – S1 energy gap (ca. 0.9 eV), slowing down the rate of S2 → S1 internal conversion. The photoluminescence behavior of the ESIPT–incapable zinc(II) coordination compounds strongly depends on the halide anion: the chlorido complex exhibits only fluorescence, the bromido complex displays a minor phosphorescence channel in addition to a major fluorescence channel, while the iodido complex exhibits predominantly phosphorescence. As a result, the emission color of the [Zn(HL4,2,Me)X2] complexes changes gradually from blue for X = Cl to orange for X = I, providing a platform for the fine-tuning of emission by the halide anion.