Six new zinc-1,3,5-benzenetricarboxylate-based metal-organic frameworks (MOFs) have been successfully synthesized using three different surfactants (PEG 400, octanoic acid, and hexadecyltributylphosphonium bromide) as reaction media. These surfactants with different characteristics, such as being neutral, acidic, and cationic, have been demonstrated to show strong effects on directing the crystals' growth and resulted in different secondary building units (SBUs) including an unusual SBU unit [Zn4(μ4-O)(CO2)7]. Our results clearly indicated that the surfactant-thermal method could offer exciting opportunities for preparing novel MOFs or other inorganic crystalline materials with diverse structures and interesting properties.