In this paper, blow-up solutions of autonomous ordinary differential equations (ODEs) which are unstable under perturbations of initial conditions are studied. Combining dynamical systems machinery (e.g. phase space compactifications, time-scale desingularizations of vector fields) with tools from computer-assisted proofs (e.g. rigorous integrators, parameterization method for invariant manifolds), these unstable blow-up solutions are obtained as trajectories on stable manifolds of hyperbolic (saddle) equilibria at infinity. In this process, important features are obtained: smooth dependence of blow-up times on initial points near blow-up, level set distribution of blow-up times, singular behavior of blow-up times on unstable blow-up solutions, organization of the phase space via separatrices (stable manifolds). In particular, we show that unstable blow-up solutions themselves, and solutions defined globally in time connected by those blow-up solutions can separate initial conditions into two regions where solution trajectories are either globally bounded or blow-up, no matter how the large initial points are.