Rod-like MIDA boronates form smectic mesophases, while wedge-shaped MIDA boronates self-assemble into columnar mesophases. However, the phase behavior of mixtures is less understood. In order to obtain further insight on the molecular self-assembly of MIDA boronate mixtures two series of binary mixtures of rod-like and wedge-shaped mesogens were prepared. The phase behavior was studied using differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffraction (XRD). The study revealed a strong dependency of the mesophase structure on the mesogen composition. Usage of a less bulky columnar mesogen suppressed the formation of columnar mesophases in the mixture and led to a decrease in melting and clearing temperatures. The phase behavior is discussed in terms of the packing parameter model typically applied for lyotropic liquid crystals.