The aluminosilicate and borosilicate MFI type zeolites were successfully synthesized by a dual-templating system using pyrrolidine tetramethylammonium hydroxide (TMAOH) as co-structure-directing agents (SDAs), in absence of inorganic cations and fluoride media. Various parameters that effect the crystallization of aluminosilicate (Al- ZSM-5) and borosilicate (B-ZSM-5) zeolites, such as the Pyrr/Si, TMA/Si and Si/Al or Si/B ratios were investigated. The obtained products were characterized by XRD, N2 Absorption,13C CP MAS NMR spectroscopy, SEM and FTIR techniques. The XRD patterns confirmed the formation a pure ZSM-5 with high crystallinity, SEM results revealed that Al-ZSM-5 and B-ZSM-5 synthesized at the same condition having different morphologies. On the other hand 13C CP MAS NMR spectroscopy confirmed the incorporation of pyrrolidine and TMA into the aluminosilicate and borosilicate zeolites products. These two kinds of SDAs played a cooperative role in the crystallisation of Al-ZSM-5 and B-ZSM-5. The role of pyrrolidine was to provide the initial nucleation and selectivity, and of TMA to provide both space-filling and basicity capacities in the synthesis.