The structural and electronic properties of a photochromic molecule dictate their potential photochemical activity. To gain insight into these influences, the ground-state structure and excited state properties of six indolylgulgides were calculated using several time dependent-density functional theory (DFT) (TD-DFT)//DFT methods, second-order M⊘ller–Plesset (MP2), and CIS(D). These methods simulated the charge-transfer properties and the conformation of the ground-state structure for each molecule. Generally, TD-DFT accurately simulated the expected charge-transfer state. The degree of spatial overlap of the occupied and virtual molecular orbitals involved in the S1 transition of indolylfulgides quantitatively assessed their charge-transfer character and was qualitatively useful in assessing their photochromic activity. The M06, M06-2X, and M11 structures were quite similar to those calculated by MP2. Structural differences, similarities, and functional trends are compared and discussed. © 2013 Wiley Periodicals, Inc.