We have investigated an electrical transport properties and electronic structure of Ce2Rh3Al9. Ce-3d and Ce-4d XPS measurements showed a clear mixed valence behavior, confirmed also by the TB-LMTO-ASA and FP-LAPW band structure calculation. A non-magnetic ground state expected from LMTO calculations seem to be in a good agreement with experimental data, however, a predicted gap of 3 meV width is not observed in resistivity ρ(T) data. Our calculations carried out for ~3% larger or smaller lattice parameters in comparison to that, experimentally obtained at room temperature lead us to conclusion that the gap is still present. We argue, that an atomic disorder could be a reason that activated behavior in ρ(t) is not observed for Ce2Rh3Al9 .