In this Letter, we report on the successful fabrication of low loss, high refractive index contrast waveguides via ion migration upon femtosecond laser writing in phosphate glass. Waveguides were produced in two different phosphate glass compositions with high and low La 2 O 3 content. In the La-rich glass, a large refractive index increase in the guiding region was observed due to the incoming migration of La accompanied by the out-diffusion of K. The much smaller refractive index change in the La-less glass is caused by rearrangements of the glass structure. These results confirm the feasibility of adapting the glass composition for enabling the laser writing of high refractive index contrast structures via spatially selective modification of the glass composition. The origin of the refractive index modification caused by femtosecond (fs) laser irradiation in phosphate glasses has been investigated by several research groups. In such reports, mostly commercial glass from Kigre, Inc. (QX and MM2) and Schott AG (IOG) are used [1][2][3][4][5]. Most of these glasses were developed for telecommunication research and industry as base materials for waveguide fabrication by Ag-Na ion exchange [6][7][8]. With the advent of fs-laser-inscription techniques, demand for new glasses grew even higher due to the ability of fast prototyping and fabrication of complex 3D custom components [5]. Still, little effort was made to optimize the glass composition for this new technique. Due to the versatility of fs-laser writing, many problems were surmounted by adjusting the processing conditions to produce excellent results in various glasses [1,5]. However, there is little doubt that glass composition is a key parameter for further optimizing fs-laser-written optical devices. Among various commercial phosphate glass compositions, we have identified and isolated a set of glass with and without La 2 O 3 to demonstrate the importance of optimizing the glass matrix composition for fs-laser writing. We show that the presence of La 2 O 3 enables us to achieve a large positive refractive index contrast (RIC) in the written structures. The responsible mechanism is identified as the migration of La to form a region of increased refractive index accompanied by out-diffusion of K. The compositional changes unambiguously correlate to positive and negative refractive index modifications. Indeed, the refractive index changes observed via La migration are far beyond what can be attributed to changes in the glass structure.In the present work, we have investigated in detail the role of La 2 O 3 in the photo-inscription mechanisms in phosphate glasses. The addition of La 2 O 3 to P 2 O 5 -Al 2 O 3 glasses is known to increase the refractive index of the glass [9,10] as well as to improve its thermal, mechanical, and optical properties. We have used two different QX special melt phosphate glass samples from Kigre, Inc., both doped with 2 wt. % Er and 4 wt. % Yb (QX was introduced as a laser glass capable of withstanding high thermal loading and shoc...