In ferromagnetic materials, spin up and down electrons can carry different heat currents. This spin-dependent energy excitation mode ('spin energy mode') occurs only when spin up and down energy distribution functions are different. In superconductors, heat is carried by quasiparticle excitations and the spin energy mode can be excited by spin-polarised current injection. In the presence of a finite Zeeman magnetic field, the spin energy mode surprisingly leads to a charge imbalance (different numbers of hole- and electron-like quasiparticles) at the superconducting gap edge. By performing spin-resolved spectroscopy of the out-of-equilibrium quasiparticle populations in a mescoscopic superconductor, we reveal that their distribution functions are non-Fermi-Dirac. In addition, our spectroscopic technique allows us to observe a charge imbalance, localised in energy to the gap edge and thus unambiguously identify the spin energy mode. Our results agree well with theory and shed light on energy transport in superconducting spintronics.