Holographic Bragg transmission gratings formed via the anisotropic phase separation of nanosized LC droplets (H-PDLC) were fabricated using thiol-ene photopolymerization. Using coherent UV laser light and a single prism, electrically switchable transmission gratings in the Bragg regime were written. The performance of the thiol-ene-based gratings were compared with those of multifunctional acrylate-based gratings written under similar conditions. Optical and electro-optical measurements suggest that thiol-ene polymers offer promise as hosts for improved H-PDLC performance. Interesting differences in the diffraction efficiencies for s– and p-probe beams are noted for the two matrices. Morphology studies by TEM and SEM exhibit striking differences in droplet shape and uniformity. These differences are speculated to be due to differences in polymer MW growth due to the step-growth propagation mechanism for thiol-enes as compared to the chain-growth propagation mechanism in multifunctional acrylates. The response times of the thiol-ene gratings were ten times slower than those of acrylates.