This paper reports on a new functionality exhibited by "polymer nanosphere multilayered organization", a new type of molecular organization, and the relationship between their structure and function. The polymer nanosphere multilayered organization is a fine structural material formed by the accumulation of single-particle layers of a hydrophobic polymer at the air/water interface; these single-particle layers have uniform height along the c-axis. By employing the "alternate compression relaxation method", high-density, low-defect particle layers are formed with a clear increase in their crystallite sizes. In the case of a ternary comb copolymer containing a carbazole ring, one particle is formed by the assembly of approximately 60 units of collapsed monolayer-like double layers. This structure is stabilized by the formation of side-chain crystals in the interlayer, with oriented pi-pi stacking of carbazole rings, resulting in enhanced fluorescence emission intensity.