Mechanical energy harvesting using Triboelectric nanogenerator (TENG) based on the coupling of electrostatic induction and contact electrification is a cost-effective and straightforward process. TENG is well known for harnessing the waste energy at a large scale. Here, we demonstrated the fabrication of enhanced-performance TENG in contact-separation mode by utilizing the facile phase inversion process for only one triboactive layer. The phase inversion is a straightforward technique to achieve films with a porous structure and high crystallinity. The non-piezoelectric, semiconducting TiO2 microparticle acts as charge trapping sites attributed to their high dielectric constant. The PVDF-10-TiO2/CA TENG showed 7 times and 10 times enhancement for voltage and short circuit current compared to the PVDF-TiO2/CA TENG prepared without phase inversion process. Furthermore, the device is a multifunctional energy harvester i.e. it can harvest biomechanical as well as wind energy. Finally, we demonstrated the use of TENG device for volatile organic compounds (VOCs) sensing. The device exhibits good response with the change in concentration as well as total flow rate. The voltage decreases with the increase in the benzene concentration. The sensitivity of as fabricated sensor is 0.0035 V/ppm concerning concentration and 0.29176 V/sccm concerning total flow rate. The sensor was integrated with the Arduino Uno for automatic detection of benzene giving the alarm warning for the presence of benzene in the environment. This work extended the application of TENG in the field of VOCs sensing, design and concept which can be applied in the future for the detection of other VOCs in the environment. © 2018