Symmetry restrictions limit the types of tasks that can be achieved with a given set of quantum states. Therefore, any breaking of these symmetries could potentially be exploited as a resource for quantum communication. Here we demonstrate this operationally by certifying asymmetry in the configuration of the Bloch vectors of a set of three unknown qubit states within the dimensionally bounded prepare-and-measure scenario. To do this, we construct a linear witness from three simpler witnesses as building blocks, each featuring, along with two binary measurement settings, three preparations; two of them are associated with the certification task, while the third one serves as an auxiliary. The final witness is chosen to self-test some target configuration. We numerically derive a bound Qmirror for any mirror-symmetric configuration, thereby certifying asymmetry if this bound is exceeded (e.g. experimentally) for the unknown qubit configuration. We also consider the gap (Qmax-Qmirror) between the analytically derived overall quantum maximum Qmax and the mirror-symmetric bound, and use it as a quantifier of asymmetry in the target configuration. Numerical optimization shows that the most asymmetric configuration then forms a right scalene triangle on the unit Bloch sphere. Finally, we implement our protocol on a public quantum processor, where a clear violation of the mirror-symmetric bound certifies asymmetry in the configuration of our experimental triple of qubit states.