Crystals of the newly synthesized compound Ca3LiOsO6 were grown by a flux method using LiCl and KCl, followed by single-crystal X-ray diffraction (XRD), low-temperature powder XRD, and measurements of ac and dc magnetic susceptibility and specific heat. The data indicate that Ca3LiOsO6 has a fully opened electronic gap with an antiferromagnetic ordered state, consistent with suggestions from the first-principles study. The observed magnetic transition temperature is 117 K, too high to be caused only by a direct spin spin interaction. It appears that the original superexchange magnetic path Os-O-Os is absent; thus, the extended superexchange path (Os-O) (O-Os) can be expected to be responsible for the 117 K magnetic order. If this is true, Ca3LiOsO6 would be highly valuable to study the nature of extended superexchange magnetic interactions in solids.