Herein, the impact of varying particle sizes of PbZr0.5Ti0.5O3 (PZT) powders on the ferroelectric and magnetoelectric properties of Mn0.5Zn0.5Fe2O4–PbZr0.5Ti0.5O3 multiferroic fluids is investigated. The PZT ferroelectric powders with different particle sizes (0.36, 0.28, 0.31, 0.75, 1.20 μm) are successfully prepared by altering the ball milling time. The multiferroic fluids demonstrate overall good sedimentation stability. The study finds that the dielectric constant first decreases and then increases with the reduction in particle size. The ferroelectric properties improve with the decrease in particle size and the application of a magnetic field. The multiferroic fluids with a particle size of 0.36 μm exhibit the highest polarization change (960.37%) under an electric field of 2000 Hz, 20 kV cm−1, and a magnetic field of 700 Oe. Furthermore, the magnetoelectric coupling coefficient first increases and then decreases with the reduction of the ferroelectric particle size. The multiferroic fluids with a particle size of 0.36 μm demonstrate the highest magnetoelectric coupling coefficient of 17.22 V cm−1 Oe−1 at 2000 Hz, indicating superior magnetoelectric coupling performance. These findings provide valuable insights into optimizing multiferroic fluids for applications requiring a high magnetoelectric coupling effect.