ErCrO3 samples were synthesized by solid state method. The structure, optical, magnetic, dielectric and low-temperature pyroelectric properties of the system were investigated. X-ray diffraction (XRD) and scanning electron microscopy (SEM) revealed that the sample has an orthorhombic structure with the Pbnm space group, and an average particle size of 641 nm. Optical studies show that the optical band gaps are 2.1 eV and 3.2 eV for the sample. DC and AC magnetization indicate that ErCrO3 undergoes three magnetic phase transitions near TN (Cr3+), TSR, and TN(Er3+). Interestingly, another hump is observed in the range of 50–70 K during the AC magnetization measurements. Dielectric and pyroelectric measurements demonstrate significant anomalies in the dielectric permittivity and pyroelectricity around TN, TSR and the corresponding temperature of the hump. This suggests a close correlation between the dielectric and pyroelectric properties with the magnetic transition. Furthermore, the pyroelectric measurements at low temperatures prove that the magnetic field could regulate the electric polarization, a further proof of the strong magnetoelectric coupling effect in the system. These properties of ErCrO3 make it have significant applications in optoelectronic devices, storage devices, sensors, and so on.