An experimental and computational investigation of the unsteady separation behaviour of two spheres in Mach-4 flow is carried out. The spherical bodies, initially contiguous, are released with negligible relative velocity and thereafter fly freely according to the aerodynamic forces experienced. In experiments performed in a supersonic Ludwieg tube, nylon spheres are initially suspended in the test section by weak threads which are detached by the arrival of the flow. The subsequent sphere motions and unsteady flow structures are recorded using high-speed (13 kHz) focused shadowgraphy. The qualitative separation behaviour and the final lateral velocity of the smaller sphere are found to vary strongly with both the radius ratio and the initial alignment angle of the two spheres. More disparate radii and initial configurations in which the smaller sphere centre lies downstream of the larger sphere centre each increases the tendency for the smaller sphere to be entrained within the flow region bounded by the bow shock of the larger body, rather than expelled from this region. At a critical angle for a given radius ratio (or a critical radius ratio for a given angle), transition from entrainment to expulsion occurs; at this critical value, the final lateral velocity is close to maximum due to the same 'surfing' effect noted by Laurence & Deiterding (J. Fluid Mech., vol. 676, 2011, pp. 396-431) at hypersonic Mach numbers. A visualization-based tracking algorithm is used to provide quantitative comparisons between the experiments and high-resolution inviscid numerical simulations, with generally favourable agreement.