Significant prior-b grain refinement of as-cast Tie6Ale4V alloy was achieved through additions of yttrium. Microstructural analysis revealed three mechanisms by which yttrium refines the prior-b grains during solidification: solute yttrium provides constitutional supercooling; yttrium scavenges oxygen and forms Y2O3 particles, which pin grain boundaries suppressing grain growth; Y2O3 particles also act as active nucleation sites. Even finer equiaxed grains were achieved through laser surface remelting suggesting that yttrium additions could be an efficient b-Ti grain refiner for the Tie6Ale4V alloy processed by additive manufacturing.