First‐principles calculations are carried out to investigate the structural and electronic properties of the α modification of zinc diphosphide (α‐ZnP2). We use the conjugate gradient (CG) minimization method, in which both the local density approximation (LDA) and the generalized gradient approximation (GGA) as implemented in the SIESTA code are employed. The ground state properties such as the lattice parameters, bulk modulus, pressure derivative of the bulk modulus at zero pressure, bond lengths and bond angles are determined and compared with the available experimental data. The energy band structure and electron density of states (DOS) of α‐ZnP2 are also presented. By analyzing the electronic band structure, a band gap of 1.91 eV is obtained. Based on the study of properties of α‐ZnP2 at high pressure, it is found that the structural and electronic properties of α‐ZnP2 at high pressure are quite stable. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)