Stepwise two-photon processes not only have great potential for efficient light harvesting but also can provide valuable insights into novel photochemical sciences. Here we have designed a [2.2]paracyclophane-bridged bis(imidazole dimer), a molecule that is composed of two photochromic units and absorbs two photons in a stepwise manner. The absorption of the first photon leads to the formation of a short-lived biradical species (half-life = 88 ms at 298 K), while the absorption of the additional photon by the biradical species triggers a subsequent photochromic reaction to afford a long-lived quinoid species. The short-lived biradical species and the long-lived quinoid species display significantly different absorption spectra and rates of the thermal back-reaction. The stepwise two-photon excitation process in this photochromic system can be initiated even by incoherent continuous-wave light irradiation, indicating that this two-photon reaction is highly efficient. Our molecule based on the bridged bis(imidazole dimer) unit should be a good candidate for multiphoton-gated optical materials.