Photophysical processes in conjugated polymers are influenced by two competing effects: the extent of excited state delocalization along a chain, and the electronic interaction between chains. Experimentally, it is often difficult to separate the two because both are controlled by chain conformation. Here we demonstrate that it is possible to modify intra-chain delocalization without inducing inter-chain interactions by intercalating polymer monolayers between the sheets of an inorganic layered matrix. The red-emitting conjugated polymer, MEH-PPV, is confined to the interlayer space of layered SnS2. The formation of isolated polymer monolayers between the SnS2 sheets is confirmed by X-ray diffraction measurements. Photoluminescence excitation (PLE) and photoluminescence (PL) spectra of the incorporated MEH-PPV chains reveal that the morphology of the incorporated chains can be varied through the choice of solvent used for chain intercalation. Incorporation from chloroform results in more extended conformations compared to intercalation from xylene. Even highly twisted conformations can be achieved when the incorporation occurs from a methanol:chloroform mixture. The PL spectra of the MEH-PPV incorporated SnS2 nanocomposites using the different solvents are in good agreement with the PL spectra of the same solutions, indicating that the conformation of the polymer chains in the solutions is retained upon intercalation into the inorganic host. Therefore, intercalation of conjugated polymer chains into layered hosts enables the study of intra-chain photophysical processes as a function of chain conformation.