Micro-structured cellular polydimethylsiloxane (PDMS) materials were prepared by a low-cost molding process allowing us to control geometry and sample size. Cellular structures are charged with a triangular quasi-static voltage with amplitudes between 1 kV and 4 kV and a frequency of 0.5 Hz fixed after having evaluated the conditions enhancing the piezoelectric response of the cellular PDMS. The piezo-electret PDMS material charged at room temperature has a piezoelectric coefficient d 33 of 350 pC/N, which is ten times larger than that of polyvinylidene fluoride. The high piezoelectric coefficient with a very low elastic modulus of 300 kPa makes these materials very useful for wearable device applications. The piezoelectric coefficient d 33 of the samples poled at high temperatures improves thermal stability but reduces PDMS piezo-electret piezoelectricity, which is explained by the structure's stiffness. These results are useful and allow us to set the conditions for the preparation of the piezo-electret materials according to desired applications.