A diphenyloctatetraene (DPOT) doped bibenzyl crystal is a model system for studying the spectroscopic properties of polyenes because the well-defined local environment of the DPOT eliminates most of the inhomogeneous broadening that obscures many transitions. The spectra of the three DPOT sites in this host are measured with site-selective laser spectroscopy to define the vibrational, electronic, and vibronic states of the S-0, S-1, and S-2 electronic states. Multiply resonant four-wave mixing spectra were then obtained using a coherent anti-Stokes Raman spectroscopy method (CARS) for a series of different laser frequencies in order to define the CARS excitation profile (CEP). The CEP profile of the C=C and C-C stretch vibrations showed strong enhancement of the four-wave mixing from the S-2 State but only the C=C stretch mode had observable enhancement from the S-1 state. Contrary to previous studies in pentacene, azulene, and perylene, DPOT did not exhibit enhancement of vibronic transitions that would permit mode selective or site-selective nonlinear spectroscopy.