I provide an explicit construction of spectral curves for the affine E8 relativistic Toda chain. Their closed-form expression is obtained by determining the full set of character relations in the representation ring of E8 for the exterior algebra of the adjoint representation; this is in turn employed to provide an explicit construction of both integrals of motion and the actionangle map for the resulting integrable system. I consider two main areas of applications of these constructions. On the one hand, I consider the resulting family of spectral curves in the context of the correspondences between Toda systems, five-dimensional Seiberg-Witten theory, Gromov-Witten theory of orbifolds of the resolved conifold, and Chern-Simons theory to establish a version of the B-model Gopakumar-Vafa correspondence for the slN Lê-Murakami-Ohtsuki invariant of the Poincaré integral homology sphere to all orders in 1/N. On the other, I consider a degenerate version of the spectral curves and prove a one-dimensional Landau-Ginzburg mirror theorem for the Frobenius manifold structure on the space of orbits of the extended affine Weyl group of type E8 introduced by Dubrovin-Zhang (equivalently, the orbifold quantum cohomology of the type-E8 polynomial CP 1 orbifold). This leads to closed-form expressions for the flat coordinates of the Saito metric, the prepotential, and a higher genus mirror theorem based on the Chekhov-Eynard-Orantin recursion. I will also show how the constructions of the paper lead to a generalisation of a conjecture of Norbury-Scott to ADE P 1-orbifolds, and a mirror of the Dubrovin-Zhang construction for all Weyl groups and choices of marked roots. Contents