Over the past two decades, fiber laser technologies have matured to such an extent that they have captured a large portion of the commercial laser marketplace. Yet, there still is a seemingly unquenchable thirst for ever greater optical power to levels where certain deleterious light-matter interactions that limit continued power scaling become significant. In the past decade or so, the industry has focused mainly on waveguide engineering to overcome many of these hurdles. However, there is an emerging body of work emphasizing the enabling role of the material. In an effort to underpin these developments, this paper reviews the relevance of the material in high power fiber laser technologies. As the durable material-of-choice for the application, the discussion will mainly be limited to silicate host glasses. The discussion presented herein follows an outward path, starting with the trivalent rare earth ions and their spectroscopic properties. The ion then is placed into a host, whose impact on the spectroscopy is reviewed. Finally, adverse interactions between the laser lightwave and the host are discussed, and novel composition glass fiber design and fabrication methodologies are presented. With deference to the symbiosis required between material and waveguide engineering in active fiber development, this review will emphasize the former. Specifically, where appropriate, materials-based paths to the enhancement of laser performance will be underscored.