The development of functional materials towards mechanical energy harvesting applications is rapidly increasing during this decade. In this study, we are reporting the mechanical energy harvesting properties of free-standing carbyne-enriched carbon film (prepared via dehydrohalogenation of PVDF). Physico-chemical characterizations such as X-ray diffraction, Fourier-transformed infrared spectroscopy, X-ray photoelectron spectroscopy, 13C NMR spectroscopy, and laser Raman spectral analyses confirmed the formation of the carbyne-enriched carbon film. The Raman mapping analysis revealed the homogeneous distribution of cumulenic (β-carbyne) networks in carbonoid matrix of the prepared film. The mechanical energy harvesting properties of carbyne-enriched carbon film have been examined under various applied compressive forces. The carbyne-enriched carbon film based energy harvester generates a peak to peak voltage of 6.48 V using a periodic force of 0.2 N, and the output voltage is directly proportional to the levels of applied compressive force. The carbyne-enriched carbon film based energy harvester possesses an instantaneous power density of about 72 nW cm−2 with excellent electromechanical stability. These experimental findings ensure the use of carbyne-enriched carbon film as a mechanical energy harvester for the first time, which can create new insights towards the development of carbon-based mechanical energy harvesters.