Abstract Hydrothermally synthesized ZSM-5 zeolites using tetrapropyl-ammonium bromide (TPA-Br), Xylitol (Xy) and tetrapropyl-ammonium bromide + Xylitol templates; those compared with that of the parent having the same Si/Al molar ratio (64) and purchased from Mobil, were characterized with several physicochemical techniques including N2 adsorption, XRD, TG/DSC, FTIR and pyridine- FTIR. The effect of various templates on the crystallinity, crystallites size, surface properties and thermal stabilities of the produced ZSM-5 were investigated. ZSM-5 synthesized using TPA-Br + Xy; of SBET = 393 m2 g–1, exhibited a crystallinity percentage comprises of 142% when compared with that of the parent (taken at 100% crystallinity) and measured as well a crystallites size of 61 nm exceeding that derived from Xy (41 nm) that measured the lowest crystallinity percentages (71%), lowest SBET (303 m2 g–1) and highest yield (65%) between all samples. The former sample showed high thermal stability (till 1,000 C) when compared with that derived from TPA-Br, as illustrated from TG/DSC thermograms that provided a criteria on decreasing the pore radius as a result of enclosing appreciable amounts of TPA+ and Xy inside narrow pores of ZSM-5. This sample also indicated a hydrophobic tendency when compared with that devoted from TPA-Br. Pyridine adsorption measurements showed that addition of Xy to TPA-Br stimulate the existence of basic sites in addition to acidic ones (mainly Bro¨ nsted ones) that was in the middle between that derived from Xy and TPA-Br templates. More infomations on the textural properties, morphologies, vibrational tetrahedral co-ordination T(Si or Al)–O modes and acidity were evaluated and discussed.