The morphology and photoluminescence properties of electrospun poly(9-vinylcarbazole) (PVK)/poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) blend fibers, which were loaded with either halloysite clay nanotubes (HNTs) or an organically modified montmorillonite (OMMT) clay, were studied by scanning electron microscopy, transmission electron microscopy, and fluorescence spectroscopy. A concentration range of 0-30 wt.% was used for the clays, while the MEH-PPV concentration was fixed at 0.5 wt.%. Both clays, especially the OMMT clay, increased the phase separation of the components in the electrospun PVK/MEH-PPV blend fibers. This was attributed to their selective localization on the polymer phases. The HNTs and OMMT clay also increased energy transfer to the lowest energy states of MEH-PPV generated during electrospinning, and modified the amount of the partially overlapping conformation of carbazole groups (p-PVK) that constrained the aggregation of the PVK chains. These changes resulted in an increased emission from p-PVK, which varied depending on the type and concentration of the clay.