Ethynylbenziodoxolones (EBXs) have recently emerged as potent reagents for the alkynylation of radicals. Their combination with photocatalysis allows the synthesis of valuable alkynes at room temperature. Herein, we discuss two photomediated strategies for the synthesis of internal alkynes. The first transformation is a 1,2-oxyalkynylation of N- and O-alkenes using 4CICzIPN as a photocatalyst. The second strategy makes use of EBXs as strong photooxidants allowing the oxidation of a variety of substrates with no need for a photocatalyst.