The use of poly(vinyl alcohol) (PVA) and a PVA-sodium dodecyl sulfate mixture (PVA-SDS) for the colloidal stabilization of poly(dl-lactide) (PDLLA) and poly(dl-lactide-co-glycolide) (PLGA) nanoparticles (NPs) loaded with paclitaxel (PTX) was investigated. During the preparation of PDLLA and PLGA NPs via a single emulsion method, electrosteric-like stabilization imparted by the PVA-SDS led to the formation of smaller average particle diameter (Dp) than using only PVA which provided steric stabilization. It was found that, with the polymer composition of the NPs, the release profile can be tuned also, depending on whether PVA-SDS or PVA alone was used as stabilizer. The mechanism of the NP degradation and PTX release was studied as a function of time. The results obtained during 28 days were discussed in detail based on the evolutions of Dp, polymer molecular weight and its polydispersity index including the role of the electrosteric-like and steric stabilizers on the phenomenology involved.