Rare-earth orthovanadates ($R{\mathrm{VO}}_3$), particularly ${\mathrm{GdVO}}_3$, exhibit emergent functional properties due to the strong interplay of spin, orbital, and lattice degrees of freedom. However, synthesizing ${\mathrm{GdVO}}_3$ not only requires a relatively challenging ${\mathrm{H}}_2/{\mathrm{N}}_2$ environment at high temperature, but also its electronic and magnetic structure remains to be clearly resolved. Here, we demonstrate an easily accessible solid-state synthesis route to prepare phase-pure ${\mathrm{GdVO}}_3$ samples in high-vacuum sealed quartz tubes. Thereby, we elucidated the temperature-dependent structural and magnetic phases by combining several experimental techniques along with first-principles calculations. We observe two distinct antiferromagnetic transitions: one due to the Gd-sublattice at $\sim 9$ K (associated with a small temperature hysteresis $\sim 1.4$ K, confirming its first-order nature), and another due to the V-sublattices at $\sim 120$ K. ${\mathrm{GdVO}}_3$ is found to exhibit a large magnetocaloric effect, with a maximum magnetic entropy change of $\approx 28$ J ${\mathrm{kg}}^{-1} {\mathrm{K}}^{-1}$ ($H$ = 5 T) at the Gd-sublattice ordering temperature. It is worth noting that this value is significantly higher than those reported for bulk rare-earth orthovanadates and manganates. Interestingly, a first-order magnetic-field-driven metamagnetic transition below $\sim 8$ K leads to a sign reversal in the magnetic entropy change from inverse to conventional magnetocaloric effect for magnetic fields beyond $\sim$ 2.5 T. Importantly, the large magnetocaloric effect around 9 K originates due to the enhancement of magnetic susceptibility as temperature decreases toward 9 K.

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• Magnetocaloric effect
• Structural properties
• Polycrystalline materials
• First-principles calculations
• Magnetization measurements
• X-ray diffraction
• X-ray photoelectron spectroscopy