Multiferroics have received considerable interest over the last decade due to the fascinating fundamental phenomena and potential use in various applications, such as low-power electronics and spintronics. Among those, investigations have focused on the coexistence of ferroelectric and ferromagnetic materials. Here, we report the rare case that the para-to ferroelastic ordering transition in antiferromagnet Mn2V2O7 occurred at TS = 260–280 K, verified by temperature-dependent magnetization measurements, dielectric, differential scanning calorimetry, and macroscopic strain-stress hysteresis loops. Furthermore, this transition was accompanied by a structural transition from the high-temperature C2/m monoclinic phase (β-phase) to a low-temperature P1¯ triclinic phase (α-phase), as identified by temperature-dependent X-ray diffraction. Consequently, TS can be successfully increased by Co- and Ni-doping and decreased by Ca-doping. Thus, the phase diagram was established for the structural stability of (Mn1-xAx)2V2O7 (A = Co, Ni, and Ca). In addition, the physical and chemical pressure effects were applied on (Mn1-xCax)2V2O7 to correlate the ferroelastic (TS) and antiferromagnetic (TN) orderings. Consequently, the magnetoelastic coupling was revealed, and a unique multiferroic material (Mn2V2O7) with a ferroelastic and antiferromagnetic ordering was obtained.