Epoxidation of two butane isomers (1-butene and isobutene) on the commercial titanium silicate (TS-1) catalyst was studied in a laboratory-scale trickle bed reactor. The transient step response technique was used as the main tool in the investigation. The transient responses revealed different dynamics of product formation in continuous operation. The study of isomers showed the impact of the molecular structure on the transient and stationary states of the system. The four-carbon chain present in 1-butene displayed a dynamic behavior with a prominent maximum of the conversion as a function of time-on-stream. On the contrary, the behavior of isobutene was displayed to be closer to ethene and propene under similar conditions reaching a steady state after ca. 2 h. The structure of the epoxide was an important factor in order to achieve a high epoxide selectivity. In isobutene epoxidation, the primary product 1,2-epoxy-2-methylpropane was highly reactive, giving a spectrum of parallelly formed byproducts. Therefore, the selectivity of the epoxide from isobutene was limited to ca. 70%. In the epoxidation of 1-butene, 1,2-epoxybutane was displayed to be a highly stable product with a selectivity close to 99%. Based on the transient and stationary data, a reaction mechanism was proposed for the epoxidation and ring-opening reactions present in the system.