The fabrication of a new-type of Silicon nanoparticles (Si-n/p) doped silica fiber is reported. The method is entirely based on the MCVD process, with no solution-doping technique being required. The TEM, EPMA, EDX, and electron diffraction analyses as well as the Raman, optical absorption, and fluorescence spectra’ measurements confirm the formation of Si-n/p in the fiber. When pumped at 406 nm, this fiber fluoresces mainly in the VIS to near-IR spectral range and the fluorescence shows a multi-peak spectral structure in several wide bands. As a consequence of the high nonlinearity of the fiber, effective supercontinuum generation at 1.6- excitation by tens ns-range, kW-level pulses is demonstrated.