In this experiment, the effect of pulsed electric field (PEF) technology on the extractability of anthocyanins and polyphenols in early-harvested Sangiovese red grapes (16.9°Bx sugar, 3.26 pH, and 10.4 g/L titratable acidity) from Emilia Romagna (Italy) was investigated. Electric field strengths were in the range of 0.9–3 kV/cm, generated by the application of short, high-voltage pulses, and the grapes were subjected to specific energies from 10.4 to 32.5 kJ/kg immediately after crushing and destemming to produce a pre-fermentative pulsed electric field treatment on a pilot scale. Grape musts and wines were analyzed for color components and polyphenols content from pressing of juices up to 3 months from the end of the fermentation of wines. Furthermore, the freshly-fermented wines were subjected to accelerated aging conditions (i.e., warming under 40 °C for 32 days) to simulate the evolution of color parameters with time. The color intensity was generally higher in treated musts and wines compared to the control, further increased by raising the intensity of the electric field. Results suggested the potentialities of pulsed electric fields (PEFs) as a mild pre-fermentative process to assist maceration and to increase the polyphenolic content of musts obtained by early-harvested Sangiovese grapes.