In this paper, we study homogeneous Einstein (α,β)-metrics on compact Lie groups and spheres. We first show that any left invariant Einstein (α,β)-metric on a connected compact simple Lie groups except with vanishing S-curvature must be a Randers metric. Secondly, we prove that any c5dcab0fccc57c3880422a206572b28">-invariant Einstein (α,β)-metric on c6d1539830f07993f323b" title="Click to view the MathML source">S4n+3(n∈N+) with vanishing S-curvature is either a Randers metric, or -invariant. Finally, we give a complete description of -invariant Einstein Finsler metrics on c55a8c8341c0cc4436" title="Click to view the MathML source">S2n+1(n≥2).