Engelhard titanosilicate-10 (ETS-10) was synthesized via hydrothermal crystallization using TiO2 and colloidal silica or water glass solution as sources of Ti and Si respectively. The synthesis was performed in the absence of organic template and seeds. Germanium substituted ETS-10 (ETGeS-10) can be directly synthesized at Ge/Ti mole ratio of 0.15 to 0.5. In addition, base-modified ETS-10 was able to be prepared by ion-exchange and impregnation methods with sodium compounds to increase the basic strength and basic site of catalyst. The synthesized products were characterized using XRD, SEM, DR-UV, ICP-AES, AAS and N2 adsorption techniques. The catalyst consists of ETS-10 with cubic-liked particles and pore size around 0.6 nm. The excess loading of germanium leads to the structural destruction of catalyst. All synthesized products were applied to transesterification reaction of palm oil with methanol to products were applied to transesterification reaction of palm oil with methanol to produce fatty acid methyl esters (biodiesel). The various reaction conditions such as catalyst amount, methanol to oil mole ratio including reaction time and temperature were studied. Biodiesel yield and glycerol were analyzed by GC technique. The highest transesterification activity was achieved when the Na-exchanged ETS-10 and Na-impregnated ETS-10 were used as catalyst, the methyl ester yield can be reached to 77.57% and 79.80%, respectively. Moreover, catalytic activities of regenerated and Na-reloaded catalysts were also investigated.