We investigate the morphology of femtosecond laser, single pulse-inscribed, point-by-point (PbP) fiber Bragg gratings. Direct measurement of a PbP grating’s refractive index profile was carried out with micro-reflectivity analysis. PbP gratings were imaged at sub-micrometer scale with scanning electron microscopy, Raman and photoluminescence studies were performed to probe the structural and electronic changes. Comparison of results from different characterisation techniques suggests that the creation of an increased refractive index region around the micro-void is due to contributions from both densification and the formation of highly polarizable non-bridging oxygen bonds.