In the present work, fiber mats of poly(lactic acid), PLA, plasticized by different amounts of oligomer lactic acid, OLA, were obtained by electrospinning in order to investigate their long term hydrolytic degradation. This was performed in a simulated body fluid for up to 352 days, until the complete degradation of the samples is reached. The evolution of the plasticized electrospun mats was followed in terms of morphological, thermal, chemical and crystalline changes. Mass variation and water uptake of PLA-based electrospun mats, together with pH stability of the immersion media, were also studied during the in vitro test. The results showed that the addition of OLA increases the hydrolytic degradation rate of PLA electrospun fiber mats. Moreover, by adding different amounts of OLA, the time of degradation of the electrospun fiber mats can be modulated over the course of a year. Effectively, by increasing the amount of OLA, the diameter of the electrospun fibers decreases more rapidly during degradation. On the other hand, the degree of crystallinity and the dimension of the α crystals of the electrospun fiber mats are highly affected not only by the presence but also by the amount of OLA during the whole process.