Herein, we introduce a nickel-photocatalyzed cross-coupling reaction between enol silyl ethers and CF3-substituted alkyl bromides. This method provides a streamlined approach for synthesizing a wide array of structurally diverse beta-CF3-substituted ketones, achieving favorable yields under mild conditions. The practicality of this methodology is further underscored by its successful application in the late-stage functionalization of various pharmaceuticals and natural products.