Novel P(VDF-TrFE)/organosilicate composite membrane was fabricated by electrospinning. The electrospun composite membrane containing as little as 2 wt% of organosilicate demonstrated significant improvements in strength, modulus, and toughness by about 103%, 45%, and 97%, respectively, when compared with those of electrospun pure P(VDF-TrFE) membrane, while maintaining high porosity and good breathability and piezoelectricity. We believe that such an organosilicate-reinforced durable, porous, and piezoelectric P(VDF-TrFE) membrane has huge advantages in various applications such as flexible sensors, wearable electronics, filter membrane, tissue engineering, battery separator, and polymer electrolyte.