A method of fabricating an optical fiber incorporating a volatile constituent, involving: (a) providing a preform comprising a cladding glass having an axial aperture and a core glass arranged in the axial aperture, wherein the working temperature of the core glass lies below the working temperature of the cladding glass; and (b) drawing the preform into an optical fiber at a drawing temperature that lies between the working temperatures of the core and cladding glasses and above the softening temperature of the cladding glass, wherein the core glass prior to drawing includes a dioxide or higher oxide compound of the volatile constituent having a Gibbs free energy of disassociation into a monoxide compound of the volatile constituent that is negative at the drawing temperature, whereby the dioxide or higher oxide compound tends to disassociate into the monoxide compound during drawing. The volatile constituent may be Sn or Pb. The method may also be adapted for incorporating P as the volatile constituent. With this method, the core material melts while the cladding glass remains solid but in a deformable state. Melting the core material, provides more freedom in the choice of combinations of core and cladding glasses. The starting material for the core may be a powder or a solid rod, i.e. the invention may be embodied as a powder-in-tube (PIT) or a rod-in-tube (RIT) method.