The present invention provides polymers and methods of preparing the same. In certain embodiments, the polymers comprise acrylate repeating units that have been derivatized (e.g., reduced and/or substituted) to form new polymeric structures. In certain embodiments, the polymers described herein self-assemble to form well-defined nanostructures. In some instances, the nanostructures exhibit relatively small d-spacing (e.g., a d-spacing value of 10 nm or less). Due to their properties, the polymers described herein are useful in a variety of applications including functional materials and biomedical applications.