Molecular dipole orientation is crucial to efficiently utilize the piezo- and ferroelectric polarization in polymers. Modern electronic applications of these polymer demand switching of dipoles with low voltage, which requires the dipole orientation to be perpendicular to the substrate (edge-on) rather than parallel (face-on). The 0D, 1D and 2D confinement of polymer architectures into nanoparticles, nanofibers, and thin films is a vital approach to control dipole orientation in ferroelectrics. Our findings show that for 1D (d33 ∼ 18 ± 2.2 pm/V) and 2D nanostructures (d33 ∼ 15 ± 1.5 pm/V) of poly(vinylidenefluoride-trifluoroethylene) (P(VDF-TrFE)), the molecular dipoles are edge-on, whereas for 0D, the dipoles are face-on, which would govern the ferroelectric and piezoelectric behaviour of these confined structures. The subsequent observation concludes that altering the dipole orientation allows precise modulation of surface potential and work function. The work functions of the 0D, 1D and 2D nanostructures are 4.56 ± 0.03 eV, 4.93 ± 0.51 eV and 4.68 ± 0.18 eV, respectively. The tunability of surface potential opens up the possibility of utilizing these nanostructures in single-material triboelectric series. Density functional theory (DFT)-based computations substantially support these experimental findings. This study provides a thorough understanding of the effect of molecule dipole orientation on piezo- and ferroelectric properties of P(VDF-TrFE) nanostructures.