Coupling of methyl 4-bromobenzoate with water as nucleophile gave phenol 2 in moderate isolated yield by switching to DMF as a solvent (for details, see Table in the Supporting Information). The ortho-substituted, electron-rich aryl bromide 2-(2-bromophenyl)ethanol did undergo an intramolecular C-O coupling, resulting in 2,3-dihydrobenzofurane (37). An analogous preparation of chromane and 1,4-benzodioxane was not feasible (see Table in the Supporting Information). The reason for this remains unclear, especially because chromanes were previously synthesized by reductive elimination from the corresponding nickel(II) oxametallacycles. The semi-heterogeneous dual catalytic reaction of 1,4dibromobenzene and isopropylideneglycerol afforded 38, a potential intermediate for the preparation of ketoconazole (Figure ), itraconazole, terconazole and their derivatives. The antidepressant Fluoxetine can be synthesized using this method. N-protected 3-methylamino-1-phenylpropanol reacted with 1-bromo-4-(trifluoromethyl)benzene resulting in N-acetyl fluoxetine (39) in 66%. The same catalytic system was evaluated for the coupling of thiols with aryl halides. The reaction of aryl bromides and thiols usually requires strongly reducing photoredox catalysts, whereas aryl iodides can be successfully coupled using weaker reductants. When the optimized semiheterogeneous protocol (the conduction band minimum of CN-OA-m was reported to be at -1.6 V vs. Ag/AgCl ) was applied on the reaction of methyl 4-bromobenzoate with methyl 3-mercaptopropionate, only 4% of the desired thioether were formed after 48 hours (Table ). The analogous reaction using methyl 4-iodobenzoate went to completion within 48 hours resulting in 79% isolated yield of the desired thioether (40). When 2-mercaptoethanol was used, a selective C-S bond formation (41), with no detectable amount of the corresponding etherification product was obtained. In contrast to the C-O coupling, the semi-heterogeneous C-S bond formation is not limited to primary and secondary thiols (40-42). Tertiary (43) and aromatic thiols (44, 45) also gave the desired thioethers in moderate isolated yields. This finding can be rationalized by the formation of highly reactive thiyl radicals which are proposed to add to Ni(I) intermediates in the dual catalytic thioether synthesis. The reaction rate was significantly increased by using blue LEDs with higher light intensity (for details, see Supporting Information). The coupling of methyl 4-bromobenzoate and methanol, for example, was complete after 16 hours instead of 24 (Figure ) using a modified setup. These intensified conditions were used for studying the recyclability of the heterogeneous carbon nitride material (Figure ). CN-OA-m was recycled six times, without losing its catalytic activity (Figure ), proofing its high potential for sustainable photocatalysis. In conclusion, a dual Ni/photocatalytic C-O coupling was developed using a carbon nitride semiconductor as recyclable photocatalyst with low toxicity. The semi-heterogeneous nickel/carbon nitride catalysis is an inexpensive, sustainable alternative to homogeneous protocols. The method selectively couples a broad range of electron-poor aryl bromides with primary and secondary alcohols as well as water in good to excellent isolated yields. The application of this protocol for intramolecular reactions and API synthesis was demonstrated. The same catalytic protocol can be utilized to couple aryl iodides with thiols.