In this article, a method is proposed to extract the effective constitutive parameters of bianisotropic metamaterials using Bloch modes. We consider 3-D structures that are realized by stacking identical unit layers, where each unit layer is a 2-D periodic array of metallic or dielectric elements of arbitrary shape embedded in a background dielectric medium. Bianisotropic metamaterials do not satisfy the condition of reflection symmetry of unit layers considered in previous studies. The eigenvectors and eigenvalues of the generalized transfer matrix of a unit layer are related to the Bloch modes of the structure. When only two dominant Bloch modes exist, closed-form expressions are found for effective permittivity, permeability, and magnetoelectric tensors of the medium. The effects of nondominant Bloch modes are taken into account as interface surface impedance matrices. The calculated scattering parameters of a slab of bianisotropic metamaterial are shown to be in good agreement with the results obtained from full-wave electromagnetic simulations using commercial solvers.