The minimal ingredients to explain the essential physics of layered copper-oxide (cuprates= materials remains heavily debated. Effective low energy single-band models of the copper-oxygen orbitals are widely used because there exists no strong experimental evidence supporting multiband structures. Here we report angle-resolved photoelectron spectroscopy experiments on La-based cuprates that provide direct observation of a two-band structure. This electronic structure, qualitatively consistent with density functional theory, is parametrised by a two-orbital ($d_{x^2-y^2}$ and $d_{z^2}$) tight-binding model. We quantify the orbital hybridisation which provides an explanation for the Fermi surface topology and the proximity of the van-Hove singularity to the Fermi level. Our analysis leads to a unification of electronic hopping parameters for single-layer cuprates and we conclude that hybridisation, restraining d-wave pairing, is an important optimisation element for superconductivity.
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