Axial modification of Boron (III) Subphthalocyanine bromide with 4‐hydroxy‐benzoic acid successfully led to the formation of macrocycle with anchored 4‐carboxyphenoxy groups [RsPcPHBA] (R= tBu, H) in the axial position and a new dimer [sPcPHBAsPc] as minor product. Tri‐tert‐butyl and unsubstituted subphthalocyanines bearing benzoate ([tBusPcBA], [sPcBA]), phenoxy‐group ([tBusPcOPh], [sPcOPh])) in the axial position, has been also investigated as control sPcs. All compounds were characterized by NMR, IR, UV‐Vis and Mass spectrometry. The electrochemical properties were studied using cyclic voltammetry (CV) and square wave voltammetry (SWV). Singlet oxygen generation was systematically measured for all synthesized [RsPcX] by kinetic method of chemical trap decomposition (DPBF) and by determination of phosphorescence of singlet oxygen species (at 1270 nm). Axially modified subphthalocyanines exhibit high quantum yields of singlet oxygen (1O2) generation (0.47‐0.62). The observed exceptional photostability in oxygen‐saturated ethanol or toluene solutions and high 1O2 quantum yields allows to use [tBusPcPHBA] as photocatalysts of selective oxidative transformations of organic sulfides to sulfoxides. Loading the catalyst to 9.7·10‐2 mol% made it possible to achieve complete conversion of the substrate (TON up to 1700).