High-throughput synthesis of the ferroelectric solid solution Pb(Zr1−xTix)O3 (PZT) on single Pt/Ti/SiO2/Si substrates was demonstrated using a modified molecular beam epitaxy (MBE) system. The PZT films exhibited a phase transition from rhombohehdral (R) to tetragonal (T) symmetry as a function of Zr:Ti ratio, across the substrate diagonal. This was consistent with the presence of a morphotropic phase boundary (MPB) at a Zr:Ti ratio of 0.64:0.36, different from the value of 0.53:0.47 observed for bulk ceramics. All points on the films exhibited ferroelectric hysteresis loops. The results demonstrate the feasibility of high-throughput MBE for deposition of complex ferroelectric oxides, and pave the way for further materials discovery, in particular Pb-free piezoceramics.