In this paper, we show the rapid generation of phase diagrams for block copolymer amphiphiles. We demonstrate the high-throughput approach for two separate types of amphiphilic block copolymers: One type consisting of poly(ethylene glycol)-b-poly(2-hydroxypropyl methacrylate) and the other consisting of poly(2-(dimethylamino)ethyl methacrylate)-b-poly(2-hydroxypropyl methacrylate), where each amphiphilic block copolymer was prepared by systematically varying the degree of polymerization of the hydrophobic block. These were each synthesized in 96-well plates using polymerization-induced self-assembly to rapidly generate a range of morphologies in aqueous solution. In this manner, 45 different assembled polymer samples were prepared at a time. These samples were sampled by automated picoliter volume liquid handling (piezoelectric robotic dispenser) and analyzed by automated transmission electron microscopy and automated image analysis to rapidly generate phase diagrams.