Efficiently controlling chemoselectivity during the organic transformation is an important challenge in organic synthesis.Most importantly,when studying the aspects of fundamental chemical bond formation,especially controlled divergent chemical bond formation,reactions that form C-C and C-O bonds can be regarded as an importan research focus.In the past few decades,visible-light-initiated synthetic chemistry has shown significant improvements for the construction of complicated compounds via the promotion of different functional transformations,and these synthetic transformations offer significant convenience and environmental benefits compared to more traditionally employed transition-metal catalysis.1 Recently,bromoacetylenes attracted our attention due to their photo-reactivity under visible-light irradiation.2 Accordingly,we further explored the possibility of a coupling reaction between bromoalkynes and alcohols.To our delight,propargyl alcohols and α-ketoesters were smoothly generated when the reaction was carried out under visible-light irradiation in the presence of N2 and O2(Figure 1); the chemoselectivity of the photoreaction was easily regulated by changing the reaction atmosphere.