Block polymers are an important class of materials offering unique and useful properties different from random polymers. Because of their tailored structure, these materials present synthetic challenges. For this reason, it is necessary to provide a thorough structural analysis to drive the synthetic effort. We describe an analytical methodology tative C-13 NMR, and H-1 pulsed gradient spin echo (PGSE) NMR coupled with direct exponential curve resolution algorithm (DECRA) data analysis. The combination of these complementary techniques provides a comprehensive assessment of the chemical structure of the final polymeric material, including the detection and quantification of homopolymer formation, compositional heterogeneity with molecular weight, and monomer sequencing. We present work on two different linear block polymers: poly(styrene-b-allyl) methacrylate) and poly[styrene-b-(styrene-alt-maleic anhydride)].