Multi-layer graphene (MLG) sheets were obtained by exfoliation of natural graphite flakes in chloroform. Dispersions with concentration up to 19 mg/mL were prepared. Statistical measurements of MLG sheet sizes by transmission electron microscopy showed average width and length of similar to 340 nm and 860 nm, respectively. MLG/chloroform dispersions were used to prepare poly(lactic acid) (PLA)/MLG composite fibrillar membranes by electrospinning. A homogeneous distribution of MLG into the fibers was observed by optical and scanning electron microscopies. The presence of MLG leads to the decrease in the diameter distribution of the fibers, which presented average diameter values below 500 nm. Isothermal kinetic crystallization of PLA showed to be influenced by the electrospinning process and the content of MLG sheets, which acts as nucleating agents.