A comparative analysis between a solution and a surface-mediated synthesis of heterotriangulene macrocycles is reported. The results show a preferential formation of the pi-conjugated macrocycles on surface due to two-dimensional confinement. The macrocycle prepared on a several hundred milligram scale by solution chemistry was characterized by single-crystal X-ray analysis and was furthermore extended toward next generation honeycomb species. Investigation of the photophysical and electronic properties together with the good thermal stability revealed the potential of MC6 as hole-transport material for organic electronics.