The origin of X-ray emission from the resolved kiloparsec-scale jets and hotspots of many active galactic nuclei remains uncertain, particularly where the X-ray emission is separate from the radio-optical synchrotron component. Possible explanations include synchrotron emission from a second electron population and external Compton or synchrotron self-Compton processes—alternatives which imply very different physical conditions within the jet. Until recently, X-ray studies of resolved jets and hotspots have been restricted to below ∼10 keV, often showing a hard spectral index indicating a spectral peak beyond this energy range. Here we present NuSTAR observations of the nearby powerful radio galaxy Pictor A, in which we clearly detect the western hotspot at approximately 4′ from the host galaxy, the most significant detection of hotspot emission above 10 keV to date. The NuSTAR spectrum is best fit by a single power law of index Γ = 2.03 ± 0.04; an exponential cutoff gives a 1σ lower limit on the cutoff energy of 40.7 keV. We confirm previous findings of variations in the soft X-ray flux detected by Chandra over the 2000 to 2015 period, at a significance of 6.5σ. This rises to >8σ in the common 3–8 keV band using the combined 22 yr span of Chandra and NuSTAR observations. The variability of the western Pictor A hotspot strongly confirms the previously argued synchrotron nature of the X-ray emission for the hotspot, while the lower bound to the spectral cutoff energy implies electron energies in the hotspot reach up to at least a few TeV.