Molecular dynamics Simulations aimed at better understanding of the relationship between reorientational dynamics of pendant fluorescent probes and time-resolved fluorescence anisotropy on one hand and the segmental dynamics and conformations of the main polyelectrolyte chain on the other hand were performed. The simulation results provide a basis for an interpretation of fluorescence anisotropy decay measurements which are used to monitor conformational changes. Such measurements are indirect and require independent additional information on the studied system for a reliable interpretation. Our simulation results show a relation between the experimentally available rotational correlation times and the conformational behavior of the polymer. The simulation results were compared with published experimental data on poly(methacrylic acid) and a good qualitative agreement was found. Some differences in absolute values can be attributed to differences between the simulated and experimental systems.