Multifunctional acrylate formulations containing nematic liquid crystals have been shown to form holographic polymer dispersed liquid crystal gratings (H-PDLCs) easily using ultra-violet AND/OR visible photoinitiators. Laser wavelengths of 364, 476, 488, 514, 532 and 647 nm have been used for the fabrication of the gratings. Recently, the use of a thiol-ene based monomer system has been shown to overcome some of the adverse effects like post polymerization, voltage creep, and non-uniform shrinkage incurred when using highly functional acrylate monomers. However, Bragg reflection gratings have only been demonstrated utilizing ultra-violet (UV) (363.8 nm Argon ion) photopolymerization. Using UV irradiation and single prism geometry limits the upper end of the reflection notch wavelength. In this work, we report on new visible photoinitiator systems developed for the formation of reflective H-PDLCs using thiol-ene monomers. Using these new photoinitiator systems, reflection notches have been routinely written from the visible to the near infrared (IR) regions. The visible photoinitiator systems included the photoinitiator and radical generator titanocene organo-metallic complex (commercially known as Irgacure 784 (Ciba-Geigy), Rhodamine 6G, Pyrromethene, and a radical generating organic peroxide as coinitiator. Reflection gratings were written using laser wavelengths 442, 488, and 532 nm with diffraction efficiencies (DEs) above 70%. Angle tuning allowed for gratings with reflection notches in the near IR (900-1500 nm) to be written using these initiator systems. Rhodamine 6G was found to be more efficient than the other two initiators. We discuss here this new chemistry, the morphology, and electro-optical properties of the reflection gratings.