Steady-state and time-resolved fluorescence techniques are combined with theoretical molecular dynamics calculations and applied to Study the secondary structure of some random copolymers of polyphophazenes containing phenoxy and binaphthoxy chromophoric groups. Analysis of excitation and emission spectra, suggested that 100% of the excitation energy of the phenoxy groups is fluorescence depolarization and lifetimes transferred to the binaphthoxy groups. Subsequently, this energy migrates among binaphthoxy groups along the polymer chain. This migration produces a noticeable quenching of the binaphthoxy fluorescence. The efficiency of this energy migration process increases with two features of the copolymer chain. namely, the fraction of binaphthoxy groups and the presence of helical sequences along the chain. Molecular dynamics simulations on several polymer fragments were used to obtain parameters related to the allowed energy-transfer processes. The results of these simulations are in good agreement with the conclusions obtained from the experimental measurements.