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Site‐selective transition‐metal‐catalyzed mono‐deboronative cross‐couplings of 1,2‐bis‐boronic esters are valuable methods for the synthesis of functionalized organoboron compounds. However, such cross‐couplings are limited to reaction of the sterically less hindered primary boronic ester. Herein, we report a nickel/photoredox‐catalyzed mono‐deboronative arylation of 1,2‐bis‐boronic esters that is selective for coupling of the more sterically hindered secondary/tertiary position. This is achieved by taking advantage of a 1,2‐boron shift of primary β‐boryl radicals to the thermodynamically favored secondary/tertiary radicals, which are subsequently intercepted by the nickel catalyst to enable arylation. The mild conditions are amenable to a broad range of aryl halides to give β‐aryl boronic ester products in good yields and with high regioselectivity. This method also allows stereodivergent coupling of cyclic cis‐1,2‐bis‐boronic esters to give trans‐substituted products. [ABSTRACT FROM AUTHOR]