In this work, we have employed electronic structure theories to explore the effect of the planarity of the chromophore on the two-photon absorption properties of bi-and ter-phenyl systems. To that end, we have considered 11 bi-and 7 ter-phenylbased chromophores presenting a donor−π−acceptor architecture. In some cases, the planarity has been enforced by bridging the rings at ortho-positions by −CH 2 and/or −BH, −O, −S, and −NH moieties. The results presented herein demonstrate that in bi-and ter-phenyl systems, the planarity achieved via a −CH 2 bridge increases the 2PA activity. However, the introduction of a bridge with the −BH moiety perturbs the electronic structure to a large extent, thus diminishing the two-photon transition strength to the lowest electronic excited state. As far as two-photon absorption activity is concerned, this work hints toward avoiding −BH bridge(s) to enforce planarity in bi-and ter-phenyl systems; however, one may use −CH 2 bridge(s) to achieve the enhancement of the property in question. All of these conclusions have been supported by in-depth analyses based on generalized few-state models.