We experimentally report high reflectivity on the poly(methyl methacrylate) (PMMA)-based polymer optical fiber Bragg gratings by means of a 266 nm pulsed laser and phase mask technique. In the first recipe, fiber Bragg gratings (FBGs) were manufactured with a single pulse up to 3.7 mJ. After post-annealing, a stable refractive index change up to 4.2×10-4 was obtained. In the second recipe, FBGs were inscribed by 22 pulses with a lower pulse energy of 1.4 mJ, showing a stable refractive index change of 6.2×10-4. Both behaviors may mainly be attributed to the movement of initiating radicals arising from benzyl dimethyl ketal (BDK) under UV irradiation. The high refractive index change in step-index fibers paves the way to tilted FBG manufacturing with large tilt angles potentially for biomedical applications.