Ferroelectric polymers such as poly (vinylidenedifluoride–trifluoroethylene) P(VDF-TrFE) are great alternative to conventional ceramics based non-volatile memory (NVM) devices owing to their low temperature and easy processing, compatible with flexible electronics. We have shown that the ferroelectric properties, in particular coercivity, can be dramatically improved by suitably controlling the microstructure of P(VDF-TrFE) thin films through manipulating the cooling rate of the samples after annealing between Tc and Tm. Simultaneously, for reduction of electrical leakage in the P(VDF-TrFE) devices we incorporated of poly(methyl-methacrylate) (PMMA) with ferroelectric P(VDF-TrFE) in different configurations, specifically blend of the two polymers and their bilayer stack forms and analyzed evolution of the electrical properties, in particular ferroelectric response vis-à-vis morphological changes. In addition, the presentation discusses electrical and mechanical reliability of the P(VDF-TrFE) based capacitors on flexible substrate. We also evolved a co-solvent approach to processing P(VDF-TrFE) films. The results showed that single solvents with large dipole moment yield larger polarization at lower voltages and a much improved electrical fatigue behaviour, especially when the substrates are UV ozone treated. But with co-solvents, sspecifically, at DMSO:MEK ratio of 1:1, the co-solvent derived memory devices yield a high remnant polarization (~ 8.5 µC/cm2) at low coercive field (0.52 MV/cm) along with improved piezoelectric properties, perhaps with best d33 coefficient, in excess of 60 pm/V reported thus far. Most importantly, the fatigue endurance of these cosolvent derived ferroelectric films shows a dramatic improvement with no fatigue observed until 108 cycles making them attractive for device applications. The devices were stable up to 390K.