Novel water-soluble dihydroxophosphorus(V) complexes of sulphophenyl substituted porphyrazine (6), corrolazine (7) and its pyrazine fused derivative (8) were prepared and their spectral, acid–base and photophysical properties in aqueous solutions were studied. Due to the presence of eight SO₃H groups, the compounds were fully monomeric (7 and 8) or only slightly aggregated (6) in water. Spectrophotometric titration revealed that the two stage deprotonation of axially bonded hydroxy groups can be achieved for porphyrazine 6 (pK_a1 = 5.62, pK_a2 = 9.13) and pyrazine fused corrolazine 8 (pK_a1 = 6.5, pK_a2 = 11.7), while only the first dissociation stage could be observed for corrolazine 7 (pK_a1 = 9.94). The fluorescence emission of the corrolazines 7, 8 and especially porphyrazine 6 was low in water (Φ_F = 0.086, 0.18, and 0.014, respectively) and completely quenched under basic conditions due to photoinduced electron transfer. In comparison with porphyrazine 6, the contraction of the macrocycle in the corrolazines 7 and 8 induced significant improvement of singlet oxygen production in water reaching values of Φ_Δ = 0.56 and 0.43, respectively, which makes the corrolazines promising photosensitizers for photodynamic therapy. The observed evolution of the electronic absorption spectra and fluorescence quenching observed in a basic medium was explained using the model DFT calculations (cc-pvtz basis set) performed for the dihydroxophosphorus(V) complexes of unsubstituted porphyrazine and corrolazine and their mono- and doubly deprotonated forms.