Ferroelectric memories show great potential in applications of portable electronics due to low power consumption, high reliability and fast response speed. Therefore, non-destructive readout of ferroelectric memories using the ferroelectric photovoltaic effect attracted tremendous research attention. In this investigation, flexoelectric-enhanced photovoltaic effect (FPV effect) were systematically investigated in curved 3D-printed BaTiO3/PVDF composite films. In the bending process, a strain gradient field was formed between the BaTiO3 (BTO) particles, which led to a relatively large flexoelectric effect. Compared with that of pristine PVDF, the flexoelectric coefficient of BTO/PVDF-15 (15% BTO) was increased 3.7-fold to 2.65 × 10−9 C/m. Furthermore, we found that the photovoltaic current Ipv of the BTO/PVDF-15 (15% BTO) composite film increased by 3.4 times compared with the pristine PVDF film at the same curvature. This is mainly attributed to the FPV effect. In addition, “polarization channels” were found for the first time inside nanocomposite materials using the flexoelectricity effect through 2D phase-field simulations, and the channels can be artificially controlled by simply bending the film. Most importantly, the BTO/PVDF-based composite film was designed as flexible ferroelectric memories. We demonstrated for the first time that the intensity difference of the signal for 0 and 1 of the BTO/PVDF-based memories were more than 10 times, which can be read directly using a laser. This investigation shows great promise that flexoelectricity in piezoelectric polymer nanocomposite can greatly benefit the nondestructive readout of ferroelectric memory devices.