Several new non-symmetrically substituted 4,4'-diphenyl-2,2'-bithiazole derivatives were synthesized with the use of a novel synthetic methodology comprising modified Hantzsch synthesis and palladium-catalyzed Kharash cross-coupling reaction at the key steps. Mesogenic properties of the new compounds were studied by optical and calorimetric methods. The most promising for practical applications are easily accessible non-symmetrical 4,4'-diaryl-2,2'-bithiazoles containing alkyl and alkoxy substituents at the para-positions of the aryl moieties that exhibit wide-range high-temperature smectic-C phases.