Photopolymerization and 3D printing applications upon near-UV or visible light are currently limited to both rather low polymerization speed and thin layer by layer productions (below 100 mu m) using photoinitiating systems (PIS) mainly inherited from the 1990s. Filling the need for new PIS, two pi-conjugated dithienophosphole derivatives (DTPs) are synthesized and proposed as high performance near-UV and visible light photoinitiators/photoredox catalysts for both free radical polymerization (FRP) of (meth)acrylates and cationic polymerization (CP) of epoxides (e.g., using light-emitting diode (LED) at 405 nm). Astounding polymerization initiating abilities are found, and high final reactive function conversions are obtained (for multifunctional monomers). Their utilization as materials in laser write and 3D printing experiments is especially carried out with for the first time, about 2 mm 3D printed photopolymers in a one-layer approach. A full picture of the included photochemical mechanisms is additionally given. Originally, dithienophosphole derivatives are featured as metal-free photoinitiators/photoredox catalysts.