Liquid crystalline phases are commonly formed by anisometric molecules or by amphiphilic materials. Despite the fact that the synthesized compounds (pentaerythol derivatives, acylated polyhydroxy compounds and aminoalcohols, a tetraphenylmethan derivative, a tetraphenylstanne) have neither a specific anisometric shape nor a strong amphiphilicity, some of them show columnar liquid crystalline mesophases. The mesogenity is mainly driven by micro segregation of the incompatible molecular parts into well-organized different microdomains. It was shown that, in analogy to block copolymers, the mesophase stability rises on increasing the degree of incompatibility between the different molecular segments and on enlarging the number of repeat units connected with each other. The molecules described herein can be regarded as the most simple star-shaped block molecules forming liquid crystalline phases.