Polyfluorene-based copolymers such as poly(9,9-dioctylfluorene)-alt-5% [bis-N,N′-(4-butylphenyl)-bis-N,N′-phenyl-1,4-phenylenediamine] (F8-5% BSP) are efficient blue-emitting polymers with various electronic phases: F8 blue-emitting glassy phase, F8 ordered more red-emitting β-phase, and F8/BSP charge transfer (CT) state. Polymer light-emitting device performance and color purity can be significantly improved by forming β-phase segments. However, the role of the β-phase on energy transfer (ET) among glassy F8, β-phase, and F8/BSP CT state is unclear. Herein, we identify dynamic molecular conformation-controlled ET from locally excited states to either the CT state or β-phase in light-emitting copolymers. By conducting single-molecule spectroscopy for single F8-5% BSP chains, we find inefficient intra-chain ET from glassy segments to the CT state, while efficient ET from the glassy to the β-phase. Spontaneous and reversible CT on–off emission is observed both in the presence and absence of the β-phase. The density functional theory calculations reveal the origin of the on-chain CT state and indicate this CT emission on–off switching behavior could be related to molecule torsional motion between BSP and F8 units. The population of the CT state by ET can be increased via through-space interaction between the F8 block and the BSP unit on a self-folded chain. Temperature-dependent single-molecule spectroscopy confirms such interaction showing a gradual increase in intensity of the CT emission with the temperature. Based on these observations, we propose the dynamic molecular motion-induced conformation change as the origin of the glassy-to-CT ET, and thermal energy may provide the activation for such a change to enhance the ET from glassy or β-phases to the CT state.