An engineered cementitious composite (ECC) belongs to a type of high-performance fiber-reinforced materials. Fiber alignment causes the anisotropy of such materials. Herein, the influence of the fiber orientation on water and ion penetration into an ECC was studied. Fiber alignment was achieved using an extrusion approach. Water absorption, sorptivity, chloride penetration resistance, sulfate attack resistance, and freezing–thawing resistance of specimens with fiber aligned horizontally (AH), vertically (AV), and randomly (R), corresponding to the direction of the exposure surface that was studied. The results showed that fibers oriented perpendicular to the water path delayed water migration into the ECC matrix. The sorptivity was significantly affected by the fiber direction. The sorptivity of the AH specimens was 35% and 13% lower than that of the AV and R specimens, respectively. After 180 days of exposure, the chloride penetration depth of the AH specimens was 5.7 mm, which is 13.6% and 20.8% lower than that of the AV and R specimens, respectively. The sulfate ingress profile indicates that the fiber–matrix interface oriented perpendicular to the penetration path can effectively delay sulfate migration. The fiber orientation also influences the compressive strength gain under immersion conditions (Na2SO4 solution, Na2SO4 + NaCl solution, and water). Compared with the AH and R specimens, the AV specimens are more sensitive to the immersion condition. In contrast, the fiber orientation has no significant effect on ECC specimens under freeze–thaw cycles. These findings indicate that controlling the fiber alignment and orientation in an ECC can improve its durability under certain exposure conditions.