Materials with both high strength and toughness are in great demand for a wide range of applications, requiring strict design of ingredients and hierarchically ordered architecture from nano- to macro-scale. Nacre achieves such a target in the long natural evolution by alternative alignment of inorganic nanoplatelets and biomacromolecules. To mimic nacre, various strategies were developed, approaching nacre-comparable performance in limited size. How to remarkably exceed nacre in both property and size is a key issue to further the advancement of composites. Here we present liquid crystal self-templating methodology to make the next generation of ultrastrong and tough nacre-mimics continuously. The hierarchically assembled composites show the highest tensile strength (652 MPa) among nacre mimics, five to eight times as high as that of nacre (80-135 MPa), and excellent ductility with toughness of 18 MJ m(-3), one to two orders of magnitude greater than that of nacre (0.1 ~ 1.8 MJ m(-3)).