Polymer-piezoceramic composites have drawn a lot of attention for sensor and energy harvesting applications. Poling such materials can be difficult due to the electric field getting mostly distributed over the low dielectric constant matrix. During this process, the electrical matrix conductivity plays a vital role. This work shows how two different polymer materials, loaded with various piezoelectric ceramic fillers, have very different poling efficiencies simply due to their intrinsic matrix conductivity. It is shown how temperature increases the matrix conductivity, and hence, increases the piezoelectric charge constant of the composites. By choosing the proper matrix material under the proper conditions, piezoelectric composites can be poled at electric fields as low as 2 kV mm −1 , which is identical to that of bulk ceramic fillers. In addition, the matrix conductivity can be altered by aging the composites in a high humidity atmosphere, which can increase the piezoelectric charge constant in similar fashion. This is a simple method to increase the matrix conductivity, and hence the piezoelectric charge constant, without the need to add any conductive fillers into the composites, which increase complexity, and leads to an increased dielectric losses.