The diagonal and off-diagonal tensor components of the first hyperpolarizability of a series of A-shaped molecules are compared by means of ab initio and semiempirical molecular orbital calculations. The calculated results are rationalized using expressions derived from a simple valence-bond charge-transfer model in which one ground and two excited state are described as a combination of one valence-bond (VB) and two charge-transfer (CT) states. In addition to the CT character, the angle (2theta) between the two donor (D)/acceptor (A) branches is a key parameter to determine the relative magnitudes between the beta(xxz) and beta(zzz) components. In the VB-2CT model, beta(xxz) presents a maximum value for 2theta = 109.47degrees, whereas beta(xxz) and mu(z) have the same sign. On the other hand, beta(zzz) decreases monotonically with theta, and its variations with the CT character follow a curve with two extrema like for one-dimensional D/A chromophores. The ab initio and semiempirical calculations as well as the VB-2CT model show that A-shaped molecules with large first hyperpolarizability and specific eta = beta(xxz)/beta(zzz) can be designed in order to build phase-matchable second-harmonic generation crystals.