This paper reports the effect of process orientation on the mechanical behavior and piezoelectricity of electroactive paper (EAPap) made from natural cotton pulp. EAPap is fabricated by a casting and wet drawing of cellulose film after dissolving cotton with LiCl and DMAc solvent. During the fabrication, permanent wrinkles, a possible factor for performance deterioration, were found in the films. Finite element method was introduced to identify the formation mechanism behind the wrinkles. The simulation results show that the wrinkles were caused by buckling and are inevitable under any conditions. The tensile and piezoelectric tests show that the orientation dependency of the stretched EAPap gives the anisotropic characteristics on both mechanical and piezoelectric properties. In this research, the anisotropic elastic moduli and Poisson's ratios are reported. The piezoelectric charge constant of EAPap in the linear elastic is calculated. The piezoelectric charge constants of EAPap are associated with the alignment angle in the order of 45° > 0° > 90° due to the strong shear effect. The higher stretching ratio gives the higher piezoelectricity due to the alignment of the molecular chains and the microstructure in EAPap. The highest piezoelectric charge constant is found to be 12 pC/N at a stretching ratio of 1.6 and aligning angle of 45°.