Energy harvesting technology allows the capturing of unused ambient energy such as solar, wind, thermal, strain and kinetic, energy of gas and liquid flows which is then converted into another form of usable energy. This paper focuses on the thermal-electrical energy harvesting based on pyroelectric effect. Pyroelectric materials generate a voltage, when subjected temperature variation. The pyroelectric polyvinylidene fluoride (PVDF) films were fabricated and characterized for pyroelectric and dielectric parameters. Using the foregoing parameters, the energy-harvesting capacity has been theoretically explored by capturing thermal energy available in the environment of Huntsville (pavement), Saudi Arabia (ambient) and MARS (ambient). The predicted maximum cumulative voltage by the end of a 300 hours cycle is approximately 0.13, 0.7 and 7.7 volts for Huntsville and Saudi Arabia and MARS, respectively for the PVDF based 10 cm2 pyro-elements. The results indicate that the electrical energy harvesting via pyroelectricity holds promise for powering autonomous low-duty electric devices. Furthermore, the mathematical modeling and numerical simulations can be helpful in designing of pyroelectric micro-power generators.