ConspectusThe past decade has witnessed significant advancements of visible-light-induced photocatalysis, establishing it as a powerful and versatile tool in organic synthesis. The major focus of this field has centered on the development of methodologies that either rely solely on photocatalysts or combine photocatalysis with other catalytic methods, such as transition metal catalysis, to address a broader and more diverse array of transformations. Within this rapidly evolving area, a subfield that we refer to as transition metal photocatalysis has garnered significant attention due to its growing impact and mechanistic uniqueness. A distinguishing feature of this subfield is the dual functionality of a single transition metal complex, which not only acts as a photocatalyst to initiate photochemical processes but also functions as a traditional catalyst, facilitating key bond-breaking and bond-forming events. As such, an exogenous photocatalyst is not required in transition metal photocatalysis. However, the implications of harnessing both the excited- and ground-state reactivities of the transition metal complex can extend beyond this simplification. One of the most compelling aspects of this area is that photoexcited transition metal complexes can exhibit unique reactivities inaccessible through conventional thermal or dual photocatalytic approaches. These distinct reactivities can be leveraged to accomplish novel transformations either by engaging an entirely different substrate pool or by unlocking new reactivities of known substrates.In 2016, our group pioneered the use of phosphine-ligated palladium catalysts that can be photoexcited upon visible-light irradiation to engage diverse substrates in radical reactions. In our initial discovery, we showed that photoexcitation can redirect the well-established oxidative addition of a Pd(0) complex into aryl iodides toward an unprecedented radical process, generating hybrid aryl Pd(I) radical species. We subsequently extended this novel strategy to the formation of alkyl radicals from alkyl halides. These reactive radical intermediates have been harnessed in a wide variety of transformations, including desaturation, alkyl Heck reactions, and alkene difunctionalization cascades, among others.Seeking to further expand this new avenue, we achieved the first example of asymmetric palladium photocatalysis in the context of allylic C-H amination, where the palladium catalyst now plays triple duty by additionally controlling the stereochemical outcome of the reaction. In parallel to reaction discovery, we have also established that diazo compounds, strained molecules, and electron-deficient alkenes can serve as alkyl radical precursors beyond organic halides and redox-active esters. Notably, the engagement of electron-deficient alkenes has been made possible by the photoinduced hydricity enhancement of Pd-H species, representing a new mode of photoexcited reactivity.This Account presents our discovery and development of visible-light-induced palladium catalysis, organized by the type of transformations explored. Given the rapid progress in the field, we anticipate that this Account will provide readers with guiding principles and inspiration for designing and developing more efficient and novel transformations.