We demonstrate by spin quantum beat spectroscopy that in undoped symmetric (110)-oriented GaAs/AlGaAs single quantum wells, even a symmetric spatial envelope wave function gives rise to an asymmetric in-plane electron Landé g-factor. The anisotropy is neither a direct consequence of the asymmetric in-plane Dresselhaus splitting nor a direct consequence of the asymmetric Zeeman splitting of the hole bands, but rather it is a pure higher-order effect that exists as well for diamond-type lattices. The measurements for various well widths are very well described within 14×14 band k·p theory and illustrate that the electron spin is an excellent meter variable for mapping out the internal—otherwise hidden—symmetries in two-dimensional systems. Fourth-order perturbation theory yields an analytical expression for the strength of the g-factor anisotropy, providing a qualitative understanding of the observed effects. © 2011 American Physical Society.