Alkynes and nitriles are valuable building blocks in organic synthesis and also have multiple applications in chemical biology and materials science. Due to the high availability of tertiary alcohols, developing methods for their conversion into alkynes and nitriles is particularly attractive. In a previous communication, our group has reported the conversion of alcohols into alkynes through cesium oxalates based on the powerful combination of photochemistry with Ethynyl BenziodoXolones (EBXs). Herein, we report further investigations into this transformation, including our findings on the effect that backbone modification of EBXs has on the deoxyalkynylation of cesium oxalates. In addition, we disclose preliminary data on the development of new deoxycyanation and dethioalkynylation processes. We also report the serendipitous discovery of the C-H alkynylation of 1,2-dichloroethane.