Understanding how complex systems respond to change is of fundamental importance in the natural sciences. There is particular interest in systems whose classical newtonian motion becomes chaotic(1-22) as an applied perturbation grows. The transition to chaos usually occurs by the gradual destruction of stable orbits in parameter space, in accordance with the Kolmo-gorov-Arnold-Moser (KAM) theorem(1-3,6-9)-a cornerstone of nonlinear dynamics that explains, for example, gaps in the asteroid belt(2). By contrast, 'non-KAM' chaos switches on and off abruptly at critical values of the perturbation frequency(6-9). This type of dynamics has wide-ranging implications in the theory of plasma physics(10), tokamak fusion(11), turbulence(6,7,12), ion traps(13), and quasicrystals(6,8). Here we realize non-KAM chaos experimentally by exploiting the quantum properties of electrons in the periodic potential of a semiconductor superlattice(22-27) with an applied voltage and magnetic field. The onset of chaos at discrete voltages is observed as a large increase in the current flow due to the creation of unbound electron orbits, which propagate through intricate web patterns(6-10,12-16) in phase space. Non-KAM chaos therefore provides a mechanism for controlling the electrical conductivity of a condensed matter device: its extreme sensitivity could find applications in quantum electronics and photonics.