Layered nanostructures (LNs) of the commercial ferroelectric Pb(Zr0.53Ti0.47)O-3 (PZT) and the natural ferroic relaxor Pb(Fe0.66W0.33)O-3 (PFW) were fabricated with a periodicity of PZT/PFW/PZT (similar to 5/1/5 nm, thickness similar to 250 nm) on MgO substrates by pulsed laser deposition. The dielectric behavior of these LNs were investigated over a wide range of temperatures and frequencies, observing Debye-type relaxation with marked deviation at elevated temperatures (> 400 K). High dielectric constant and very low dielectric loss were observed below 100 kHz and 400 K, whereas the dielectric constant decreases and loss increases with increase in frequency, similar to relaxor ferroelectrics. Asymmetric ferroelectric hysteresis loops across UP and DOWN electric field were observed with high remanent polarization (P-r) of about 33 mu C/cm(2). High imprint (similar to 5-7 V across 250 nm thin films) were seen in ferroelectric hysteresis that may be due to charge accumulation at the interface of layers or significant amount of strain (similar to 3.21) across the layers. Room temperature ferromagnetic hysteresis was observed with remanent magnetization 5.32 emu/cc and a coercive field of similar to 550 Oe. Temperature and field dependent leakage current densities showed very low leakage similar to 10(-7)-10(-5) A/cm(2) over 500 kV/cm. We observed imprint in hysteresis that may be due to charge accumulation at the interface of layers or active role of polar nano regions (PNRs) situated in the PFW regions.