Tactile sensors are widely used by the robotics industries over decades to measure force or pressure produced by external stimuli. Piezoelectric-based pressure sensors have intensively been investigated as promising candidates for tactile sensing applications. In contrast, piezoelectric-based pressure sensors are expensive due to their high cost of manufacturing and expensive base materials. Recently, an effect similar to the piezoelectric effect has been identified in non-piezoelectric polymers such as poly(d,l-lactic acid (PDLLA), poly(methyl methacrylate) (PMMA) and polystyrene. Hence investigations were conducted on alternative materials to find their suitability. In this article, we used inexpensive atactic polystyrene (aPS) as the base polymer and fabricated functional fibers using an electrospinning method. Fiber morphologies were studied using a field-emission scanning electron microscope and proposed a unique pressure sensor fabrication method. A fabricated pressure sensor was subjected to different pressures and corresponding electrical and mechanical characteristics were analyzed. An open circuit voltage of 3.1 V was generated at 19.9 kPa applied pressure, followed by an integral output charge (ΔQ), which was measured to calculate the average apparent piezoelectric constant dapp and was found to be 12.9 ± 1.8 pC N−1. A fabricated pressure sensor was attached to a commercially available robotic arm to mimic the tactile sensing.