Multiferroic behaviour in novel kind of ferroelectric (FE)–ferromagnetic (FM) particulate composites of (1−x)PbZr0.95Ti0.05O3(PZT)–(x)Ni0.7Zn0.3Fe2O4 (NZFO) [x = 0.1, 0.2, 0.3 and 0.4] has been studied. The study of FE–FM composites is represented in the context of structural, electrical, magnetic and magnetodielectric properties. X-ray diffraction reveals that both ferroelectric (PZT) and ferrite (NZFO) phases are present in prepared 0–3 type particulate composites. Scanning electron micrographs show the distribution of NZFO in the PZT matrix. Temperature-dependent relative permittivity studies revealed ferroelectric to paraelectric transition at ~ 250 °C. Room-temperature dielectric properties of the system have been studied in a wide range of frequencies (100 Hz to 1 MHz). Polarization versus electric field (P–E) studies at room temperature give conclusive confirmation of the presence of spontaneous polarization in all the composites. Magnetodielectric (MC%) measurements show the maximum 7.74% change at 1 kHz along with high values of magnetoelectric coupling coefficients γ ~ 5.98 × 10–5 (emu/g)−2, χE ~ 53.75 (mV/cm Oe) and χ ~ 16.60 × 10–8 (s/m) for 60PZT–40NZFO composite.