To describe the detailed microstructure of homogeneous ethylene-1-alkene copolymer chains and to study the characteristics of single site catalysts, Markov statistics are used to fit peak intensities of all relevant C-13 NMR signals of series of copolymers. In the case of the occurrence of inverted comonomer units, a first-order Markov terpolymer is applied, otherwise a second-order Markov copolymer model. Chain propagation probabilities are obtained via modeling of the entire NMR spectrum. This procedure results in an accurate reproduction of the chain microstructure, including ethylene, 1-alkene, and methylene sequence length distributions. If the experimental (co)monomer feeds are known, the reactivity ratios and the theoretical (co)monomer feeds are also found providing information about the copolymerization kinetics and the characteristics of the catalyst. (c) 2006 Wiley Periodicals, Inc.