Multiblock copolymers offer the possibility to combine the properties of different polymers. Thus, new materials with tailor-made unique properties are available by coupling of different suitable polymeric segments. The goal of the work discussed in this paper was to combine advantageous properties of liquid-crystalline polymers (LCP) with those of polysulfone (PSU). Therefore, liquid crystalline poly(ethylene terephthalate-co-1,4-oxybenzoates) were connected with PSU oligomers. Chemically homogeneous multiblock copolymers with high molecular weight were obtained by a melt transesterification procedure. It was demonstrated by wide angle x-ray scattering (WAXS), polarizing microscopy, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC) that the properties of the multiblock copolymers (solid phase structure, phase behavior, morphology, glass transition, and melting behavior) can be balanced by the segment length of the incorporated blocks. The investigations clearly reveal the existence of a two-phase structure. However, a change of properties compared to the corresponding homopolymers refers to certain interactions between the phases due to the chemical connection of the LCP and PSU segments.