Angle-resolved photoemission (ARPES) and optical measurements were performed on single crystal samples of LiCu2O2, an antiferromagnetic S=1/2 spin-chain compound. The ARPES spectra show several dispersive branches associated with hybrid copper-oxygen states. The occurrence of the valence band maximum halfway between the center and the edge of the Brillouin zone, and the complex spectral line shapes are not reproduced by the existing calculations of the electronic structure. We suggest that they can be interpreted within a one-dimensional scenario of strongly correlated antiferromagnetic insulators. The combination of ARPES and optics allows us to estimate the magnitude of the charge-transfer gap (Delta=1.95 eV). Moreover, the temperature-dependent optical conductivity bears signatures of the three different magnetic phases of this material.