The present invention provides a new and unique method for increasing the photosensitivity of a large diameter optical waveguide having a cross-section of at least about 0.3 millimeters. The method features loading the large diameter optical waveguide with a photosensitizing gas at a pressure at least about 4000 pounds per square inch (PSI) at a temperature of at least about 250E Celsius. The photosensitizing gas may be hydrogen, Deuterium or other suitable gas. The method also includes the step of using a particular large diameter optical waveguide having a diameter of greater than 0.9 millimeters. The method may be used as part of a process for writing a Bragg grating in an inner core or a cladding of the large diameter optical waveguide.