jats:titleAbstract</jats:title>jats:pConjugated polymers are an important class of chromophores for optoelectronic devices. Understanding and controlling their excited state properties, in particular, radiative and non‐radiative recombination processes are among the greatest challenges that must be overcome. We report the synthesis and characterization of a molecularly encapsulated naphthalene diimide‐based polymer, one of the most successfully used motifs, and explore its structural and optical properties. The molecular encapsulation enables a detailed understanding of the effect of interpolymer interactions. We reveal that the non‐encapsulated analogue jats:boldP(NDI‐2OD‐T)</jats:bold> undergoes aggregation enhanced emission; an effect that is suppressed upon encapsulation due to an increasing π‐interchain stacking distance. This suggests that decreasing π‐stacking distances may be an attractive method to enhance the radiative properties of conjugated polymers in contrast to the current paradigm where it is viewed as a source of optical quenching.</jats:p>