Steady-state fluorescence for dilute solutions of poly(N-vinyl carbazole) and N-vinyl carbazole/styrene copolymers of different molar monomer compositions upon excitation of carbazole groups were performed. I-E/I-M ratios depend on solvent nature, emission wavelength and copolymer composition. Molecular dynamics simulations on pure isotactic and sindiotactic fragments of different monomer compositions were used for identifying the amount and the conformations capable of forming intramolecular excimers. The analysis of theoretical results interprets the variation of the amount of intramolecular excimer with the molar monomer content. Types of complexes by total or partial overlapping between adjacent and non-adjacent carbazole chromophores were also distinguished.