A general strategy through the use of direct azidation of alcohols allowed the sequence control of macromers via both the iterative sequential growth and iterative exponential growth methods. The chemistry was highly efficient in building polymers from a sequence of compositionally different macromers tethered together in close proximity. Using the DPPA/DBU method for near quantitative azidation of the benzyl alcohol moiety, sequence controlled polymers were made via a direct and one-step procedure for CuAAC activation. With four different macromers, spherical miktoarm star-like polymers of 50 000 molecular weight were prepared with a low dispersity, and the polymer coil size depended on the type of added macromer. Polymers made via the iterative methods opens the way for the design of advanced materials with predictable properties.