Wearable electronics and smart harvesting textile studies require a material system that resists physical stimulation. Such applications require receptive piezo-polymers, and their activation-free preparation that can translate into a continuous large-area film. In this work, it is discussed whether the β-content of piezo-polymer is extended with no use of any activation (i.e. poling), and if the β-content increases, it can be processed over a wide range of surfaces like large-area piezo-film. Such prerequisites within polyvinylidene fluoride-molybdenum disulfide ((PVDF)-MoS2 ) piezo-polymer are thoroughly experimented here to develop a high-performance piezo-film. A MoS2 -mediated PVDF piezo-polymer (termed as P+ -MoS2 ) is introduced, in which no extra β-enhancement activation step is required after spin coating. Experimental results record β ≧ 80% which allows to harvest the voltage and current in the level of ≈17 V and 1 µA, respectively which satisfies 5 V supply voltage requirement of the current microelectronics, and internet of things (IoT). In addition, the capacitors having different capacities are charged using the developed nanogenerator to check its practical applicability. Therefore, the transition process of P-MoS2 to aligned P+ -MoS2 due to passive interlocking (PiL) through rotating directional field is novel and found to be a principal reason for β-enhancement in fabricated devices.