Consider a compact connected simple Lie group G. We study homogeneous Einstein metrics for a class of compact homogeneous spaces, namely generalized flag manifolds G/H with second Betti number b2(G/H)=1. There are 8 infinite families G/H corresponding to a classical simple Lie group G and 25 exceptional flag manifolds, which all have some common geometric features; for example they admit a unique invariant complex structure which gives rise to unique invariant Kähler–Einstein metric. The most typical examples are the compact isotropy irreducible Hermitian symmetric spaces for which the Killing form is the unique homogeneous Einstein metric (which is Kähler). For non-isotropy irreducible spaces the classification of homogeneous Einstein metrics has been recently completed for 24 of the 26 cases. In this paper we construct the Einstein equation for the two unexamined cases, namely the flag manifolds E8/U(1)×SU(4)×SU(5) and E8/U(1)×SU(2)×SU(3)×SU(5). In order to determine explicitly the Ricci tensors of an E8-invariant metric we use a method based on the Riemannian submersions. For both spaces we classify all homogeneous Einstein metrics and thus we conclude that any flag manifold G/H with b2(M)=1 admits a finite number of non-isometric non-Kähler invariant Einstein metrics. The precise number of these metrics is given in Table 1.