Communication: Long bulky substituents do not affect the nonlinear optical properties of the octopolar system 1,3,5-trihydroxy-2,4,6-trinitrobenzene (THTNB), but lend it liquid crystal (LC) properties, as demonstrated here. The synthesis of this LC derivative (see Figure for structure) is described as are its thermal, mesomorphic, and NLO properties. The advantages of NLO-active LCs are also touched upon.