We have studied the high-pressure behavior of FeVO4 by means of single-crystal X-ray diffraction (XRD) and density functional theory (DFT) calculations. We have found that the structural sequence of FeVO4 is different from that previously assumed. In particular, we have discovered a new high-pressure phase at 2.11(4) GPa (FeVO4-I'), which was not detected by previous powder XRD studies. We have determined that FeVO4, under compression (at room temperature), first transforms at 2.11(4) GPa from the ambient-pressure triclinic structure (FeVO4-I) to a second previously unknown triclinic structure (FeVO4-I'), which experiences a subsequent phase transition at 4.80(4) GPa to a monoclinic structure (FeVO4-II'), which was also previously detected in powder XRD experiments. Single-crystal XRD has enabled these novel findings as well as an accurate determination of the crystal structure of FeVO4 polymorphs under high-pressure conditions. The crystal structure of all polymorphs has been accurately solved at all measured pressures. The pressure dependence of the unit-cell parameters and polyhedral coordination have been obtained and are discussed. The room-temperature equation of state and the principal axes of the isothermal compressibility tensor of FeVO4-I and FeVO4-I' have also been determined. The structural phase transition observed here between these two triclinic structures at 2.11(4) GPa implies abrupt coordination polyhedra modifications, including coordination number changes. DFT calculations support the conclusions extracted from our experiments.