AbstractFlexible and cost‐effective poly(vinylidene fluoride) (PVDF)‐based composites having excellent piezo performance are quite interesting for developing actuators, sensors, and nanogenerators. In this work, a hybrid PVDF‐based nanocomposite consisting of a fixed quantity of titanium dioxide (TiO2) and varying quantities of reduced graphene oxide (rGO) for increased mechanical and piezoelectric performance is reported for the first time. Compared to pure PVDF, there is a significant enhancement in mechanical properties for hybrid nanocomposites. The highest piezoelectric voltage as well as current values of 10.2 V and 0.78 μA are recorded for a hybrid nanocomposite containing 1 wt% of rGO for continuous finger‐tapping operation. A multicriteria decision‐making (MCDM)‐based material selection and optimization technique called TODIM is applied, and a sensitivity study is carried out to select the best material for mechanical energy harvesting applications. A hybrid nanocomposite based on PVDF‐TiO2 with 1% rGO loading is the most suitable material according to the TODIM (an acronym in Portuguese for Interactive Multicriteria Decision Making) approach.Highlights PVDF‐TiO2‐rGO nanocomposites are fabricated by solvent casting. TODIM optimization technique is applied for the best material selection among samples. Material ranking consistency shows the reliability of the TODIM method. Conductive rGO increases interfacial polarization, resulting in enhanced ε values. An increment of 88% and 104% in tensile strength and elastic modulus, respectively.