Polymer-based multicolor emissive materials have growing demand due to their potential applications in various fields such as full-color displays, bioimaging, and light sources because of their processability and high stability. Herein, we report dual-color emissive hybrid materials based on biocompatible poly(l-lactide) and polyethylene glycol-modified two-dimensional layered double hydroxide quantum dots (PEG-LDHQDs). The morphology of polymer films tunes the spatial distribution of QDs within the polymer matrix, modulating the energy transfer between the QDs and affording the dual emission behavior in the aggregated states. The amorphous hybrid films show single emission (blue) from the finely dispersed QDs (mostly isolated) within the polymer matrix. In contrast, dual emission (blue and red) was observed when the polymer was crystallized due to the possible accumulation of QDs at the interface of crystalline and amorphous phases in the lamellar structure. Furthermore, the dual emission could be enhanced by the aggregation of QDs on the pores of the breath figure pattern constructed on the surface of the hybrid film.