Electrons in atoms possess both spin and orbital degrees of freedom. In non-relativistic quantum mechanics, these are independent, resulting in large degeneracies in atomic spectra. However, relativistic effects couple the spin and orbital motion leading to the wellknown fine structure in their spectra. The electronic states in defect-free carbon nanotubes (NTs) are widely believed to be four-fold degenerate 1-10 , due to independent spin and orbital symmetries, and to also possess electron-hole symmetry 11 . Here we report measurements demonstrating that in clean NTs the spin and orbital motion of electrons are coupled, thereby breaking all of these symmetries. This spin-orbit coupling is directly observed as a splitting of the four-fold degeneracy of a single electron in ultra-clean quantum dots. The coupling favours parallel alignment of the orbital and spin magnetic moments for electrons and anti-parallel alignment for holes. Our measurements are consistent with recent theories 12,13 that predict the existence of spin-orbit coupling in curved graphene and describe it as a spin-dependent topological phase in NTs. Our findings have important implications for spin-based applications in carbon-based systems, entailing new design principles for the realization of qubits in NTs and providing a mechanism for all-electrical control of spins 14 in NTs.Carbon-based systems are promising candidates for spin based applications such as spinqubits [14][15][16][17][18][19] and spintronics 20-23 as they are believed to have exceptionally long spin coherence times due to weak spin-orbit interactions and the absence of nuclear spin in the 12 C atom. Carbon NTs may play a particularly interesting role in this context because in addition to spin they offer a unique two-fold orbital degree of freedom that can also be used for quantum manipulation. The latter arises from the two equivalent dispersion cones (K and K') in graphene, which lead to doubly-degenerate electronic orbits that encircle the nanotube circumference in a clockwise (CW) and counter-clockwise (CCW) fashion 24 (Fig 1a). Together, the two-fold spin degeneracy and two-fold orbital degeneracy are generally assumed to yield a four-fold-degenerate electronic energy spectrum in clean NTs. Understanding the fundamental symmetries of this spectrum is at the heart of successful manipulation of these quantum degrees of freedom.A powerful way to probe the symmetries is by confining the carriers to a quantum dot (QD) and applying a magnetic field parallel to the tube axis, || B 4,5,8,10,24,25 . The confinement creates bound states and the field interrogates their nature by coupling independently to their spin and orbital moments. In the absence of spin-orbit coupling, such a measurement should yield for a defect-free NT the energy spectrum shown in figure 1b. At 0 || = B the NT spectrum should be four-fold degenerate. With increasing || B the spectrum splits into pairs of CCW and CW states