Biological tissues exhibit electrical properties, which contribute to multiple physiological processes and control cellular behaviour. It has been shown that extracellular matrix (ECM) piezoelectricity is crucial in controlling various process on the cellular level. Therefore, the use of piezoelectric materials in tissue engineering was long envisaged as a promising strategy to mimic the ECM and orchestrate cells and tissues behaviour. Piezoelectric materials have the capacity to transform loads from environment to electrical charge without the need of external powering. They can be used as actuators (produce stress or electrical charge), and deliver stimulus to cells, particularly in a dynamic flow environment such as a cardiovascular system. Multiple studies have shown that piezoelectric scaffolds can influence cells adhesion, proliferation, differentiation, morphology, and maturation. Piezoelectric scaffolds have been explored in many tissue engineering applications; however, their usability is still limited by gaps in understanding the relationships between material composition, structure, processing, post-processing, polarisation, and piezoelectric output. There were limited attempts of optimising electrical output of piezoelectrics by tuning structural and mechanical parameters of the material, which is a barrier towards successful application in biomedical field. Polarisation of piezoelectric polymers using well established methods of corona and contact poling is particularly difficult due to rapid electrical short circuit preventing from applying sufficient electrical field to align the material dipoles and unlock piezoelectric potential. In this work, we analyse the influence of processing parameters and structural properties of 3D printed PVDF-TrFE piezoelectric polymers on the capacity of polarisation using various techniques and their electrical output. We demonstrate a relationship between material porosity, its poling capacity and piezoelectric potential. We propose optimal processing parameters to achieve structures that can be efficiently polarised towards applications in tissue engineering.