In this work CASPT2 calculations of polyacenes (from naphthalene to heptacene) were performed to find a methodology suitable for calculations of the absorption spectra, in particular of the La (B2u state) and Lb (B3u state) bands, of more extended systems. The effect of the extension of the active space and of freezing σ orbitals was investigated. The MCSCF excitation energy of the B2u state is not sensitive to the size of the active space used. However, the CASPT2 results depend strongly on the amount of σ orbitals frozen reflecting the ionic character of the B2u state. On the other hand, the excitation energies of the B3u state are much more sensitive to the size of the active space used in the calculations reflecting its multiconfigurational character. We found a good agreement with experimental data for both bands by including 14 electrons in 14 π orbitals in the active space followed by the CASPT2(14,14) perturbation scheme in which both σ and π orbitals are included.