The field of palladium-catalyzed cross-coupling has seen tremendous growth since the 2010 Nobel Prize in Chemistry was awarded. Significant efforts have been made to develop highly active and selective catalysts, which have been used to realize particularly challenging cross-couplings. Beyond extending the reaction scope and tolerance of well-established Pd-catalyzed cross-coupling, novel transformations have been developed by rationally combining elementary catalytic steps with the newly invented catalyst systems. This chapter focuses largely on the discovery and recent developments of a palladium-catalyzed carboiodination reaction, which incorporates a rare Csp³–I reductive elimination as an elementary step in the catalytic cycle. As a prelude to the discussion of carboiodination, the seminal reports of carbon–halogen reductive elimination from transition metal complexes [i.e., Pd(II), Pd(IV), Pt(V) and Rh(III)], which laid the necessary groundwork for the discovery of this novel reaction, are discussed.