This work is devoted to the study of two copper complexes (Cu) bearing pyridine ligands, which were synthesized, evaluated and tested as new visible light photoinitiators for the free radical photopolymerization (FRP) of acrylates functional groups in thick and thin samples upon light-emitting diodes (LED) at 405 and 455 nm irradiation. These latter wavelengths are considered to be safe to produce polymer materials. The photoinitiation abilities of these organometallic compounds were evaluated in combination with an iodonium (Iod) salt and/or amine (e.g., N-phenylglycine—NPG). Interestingly, high final conversions and high polymerization rates were obtained for both compounds using two and three-component photoinitiating systems (Cu1 (or Cu2)/Iodonium salt (Iod) (0.1%/1% w/w) and Cu1 (or Cu2)/Iod/amine (0.1%/1%/1% w/w/w)). The new proposed copper complexes were also used for direct laser write experiments involving a laser diode at 405 nm, and for the photocomposite synthesis with glass fibers using a UV-conveyor at 395 nm. To explain the obtained polymerization results, different methods and characterization techniques were used: steady-state photolysis, real-time Fourier transform infrared spectroscopy (RT-FTIR), emission spectroscopy and cyclic voltammetry.