The in-plane effective 90° magnetization rotation of Co2FeAl thin film grown on PMN-PT substrate induced by the electric field is investigated at room temperature. The magnetic hysteresis loops under different positive and negative electric fields are obtained, which reveals remanent magnetization can be mediated by the electric field. Moreover, under positive electric fields, the obvious 90° magnetization rotation can be observed, while remanent magnetization is nearly unchanged under negative electric fields. The result is consistent with the electric field dependence of effective magnetic field, which can be attributed to the piezostrain effect in Co2FeAl/PMN-PT structure. In addition, the piezostrain-mediated 90° magnetization rotation can be demonstrated by the result of resonance field changing with electric field in the measurement of ferromagnetic resonance, which is promising for the design of future multiferroic devices.