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In the present work, a statistical study of the morphology and thermal behavior of poly(lactic acid) (PLA)/oligomer(lactic acid) (OLA)/magnesium oxide nanoparticles (MgO), electrospun fibers (efibers) has been carried out. The addition of both, OLA and MgO, is expected to modify the final properties of the electrospun PLA-based nanocomposites for their potential use in biomedical applications. Looking for the compositional optimization of these materials, a Box–Wilson design of experiment was used, taking as dependent variables the average fiber diameter as the representative of the fiber morphologies, as well as the glass transition temperature (T_g) and the degree of crystallinity (X_c) as their thermal response. The results show <r²> values of 73.76% (diameter), 88.59% (T_g) and 75.61% (X_c) for each polynomial fit, indicating a good correlation between both OLA and MgO, along with the morphological as well as the thermal behavior of the PLA-based efibers in the experimental space scanned.