We used spatially resolved photoluminescence (PL) and resonant Raman spectroscopy to study the electronic structure of single GaAs nanowires (NWs) consisting of zinc-blende (ZB) and wurtzite (WZ) segments. For narrow ZB segments and stacking faults the energy range of the observed PL peak positions is found to deviate from that of the maxima in resonance Raman profiles. These different energy ranges reflect the fact that the PL recombination is dominated by spatially indirect transitions whereas the resonance enhancement of Raman scattering is caused by direct transitions. Our results provide evidence for the type II band alignment between ZB and WZ GaAs and a coherent picture of all near-band-gap transition energies in GaAs NWs.