The effect of molecular weight and average comonomer content on the crystallization analysis fractionation (Crystaf) of ethylene/1-hexene copolymers was investigated experimentally and modeled via stochastic simulations. Molecular weight and comonomer content are the main structural parameters that affect the crystallizability of polymer molecules from dilute solutions. Sets of samples with varying molecular weight and comonomer content were prepared to study each effect separately. Although both structural parameters significantly affect the shape of Crystaf profiles, comonomer content is the main determining factor for Crystaf peak location for most molecular weights of interest. The results of the stochastic simulations show good qualitative agreement with the experimental data, but also indicate some clear limitations that might be related to the kinetics of crystallization effects during Crystaf analysis. (C) 2003 Elsevier Science Ltd. All rights reserved.