and heating to light exposure. The utility of light is particularly attractive given the ability to create micrometer-sized features at low cost using inexpensive existing projection-based Digital Light Processing (DLP) and light-emitting diode liquid crystal display (LED/LCD) technologies. Both DLP and LED/LCD methods use vat photopolymerization 3D printing, which employs light to convert liquid resins into solid objects. Although conventional lightbased 3D printing relies on high energy ultraviolet (UV) light to achieve rapid polymerization rates and correspondingly short build times (approximately seconds per layer), visible light is emerging as an attractive alternative. [11][12][13] Relative to UV light, visible light is naturally abundant, less expensive, and benign (generally reduced absorption and scattering), which gives it the potential to advance 3D printing of polymeric materials by enabling economical preparation of, for example, cell-laden hydrogels, [14] opaque composites, [15] or multimaterial structures (via wavelength selective reactions). [7,[16][17][18][19] Recently, we demonstrated that a three component photosystem comprising a visible-light-absorbing photoredox catalyst (PRC) with donor (diphenyliodonium) and acceptor (triphenyl (n-butyl) borate) co-initiators could facilitate photocuring of acrylate-based resins on timescales (approximately seconds) that were competitive with commercial UV light systems (Figure 1). [11] However, the difference in mechanism undergone by UV photoinitiators (PIs) (Type I) and visible PRCs (Type II) to generate reactive radicals results in greater oxygen sensitivity for the latter. Thus, a major limitation of highly reactive visible-light-curable resins for 3D printing is the need for oxygen removal, both from the resin and surrounding atmosphere during printing. To briefly explain the disparity in oxygen sensitivity, UV photoinitiators generate free radicals upon rapid homolytic scission from singlet photoexcited states (Type I mechanism), while efficient visible PRCs often rely on triplet photoexcited states to minimize the impact of ratelimiting electron transfer to a co-initiator for radical formation (Type II mechanism). [20][21][22] Given that molecular oxygen resides in a triplet ground state, it rapidly reacts with PRCs in their triplet-excited states, which results in a delayed onset of curing, called the oxygen inhibition period. [23] Furthermore, oxygen will quench propagating carbon centered radicals to form more stable peroxy radicals that do not reinitiate acrylate polymerizations. Thus, oxygen limits curing speed and monomer-topoly mer conversion, which necessitates its removal. [24,25] With 3D printing, the desire is to be "limited only by imagination," and although remarkable advancements have been made in recent years, the scope of printable materials remains narrow compared to other forms of manufacturing. Light-driven polymerization methods for 3D printing are particularly attractive due to unparalleled speed and resolution, yet the relianc...