Immiscibility between dimethyl sulfoxide (DMSO) and polar solvents used for poly(N-vinylcarbazole) (PVK) solutions, leads to failed light-emitting diodes when colloidal cadmium sulfide (CdS) nanoparticles capped with thiophenol are incorporated to their active layer. To prevent this, a heat treatment is applied to the CdS nanoparticles in order to evaporate DMSO solvent. After evaporation most of the nanoparticles increased their size, and some of them show hexagonal crystalline structure instead of the original cubic zinc-blende observed in colloidal pre-treated nanoparticles. Nevertheless, enhanced electronic properties are measured in light-emitting devices when DMSO-free nanoparticles are embedded in the poly(N-vinylcarbazole) active layer. Light emission from these hybrid devices comprises the whole visible range of wavelengths as searched for white LEDs. Moreover, electroluminescence from both types of CdS nanoparticles (smaller cubic and bigger hexagonal) has been discriminated and interpreted through Gaussian deconvolution.