A synthesis of 1,3,3′,5,5′-alkanoyloxy-(Ia) and 1,3,3′,5,5′-alkoxybenzoate biphenyls (Ib) has been performed. Peculiarities of phase behavior of liquid crystalline 1,3,3′,5,5′-alkoxybenzoate biphenyls (Ib) in mixtures with discotic (1-nitro-2,3,6,7,10,11-hexadecyloxytriphenylene — II and triphenylene 2,3,6,7,10, 11-hexaundecyloxybenzoate — III) and chiral (cholesterol undecylate — IV) were studied with the aim of identifying the type of mesomorphysm. Ib was found to be mutually soluble with II and III and partially soluble with IV. The construction and analysis of the phase diagram of the mixtures of I with II throughout the range of concentrations makes it possible to assign the studied biphenyl Ib to discotic mesogens. An area of the smectic phase, which is formed from the chiral nematic IV and the discotic mesogen Ib (which displays dimorphism in the mesophase) have been found for the first time in the mixtures of these compounds. During cooling, in the mixture with molar ratio 1:1 dendritic textures with grained branches are formed, which are similar to those described in literature for TGB (twist grain boundary) phases. Relying on our studies, we suggest that Ib has a columnar type of the structure in the low-temperature area and a nematic, probably chiral, type in the high-temperature area of the mesophase.