The interaction between surfactants and hydrates provides insight into the role of surfactants in promoting hydrate formation. This work aims at understanding the adsorption behavior of sodium dodecyl sulfate (SDS) on cyclopentane (CP) hydrates and its derivative surfactant on tetrabutylammonium bromide (TBAB) hydrates. Cyclopentane (CP) is a hydrophobic former whereas tetrabutylammonium bromide (TBAB) is a salt that forms semiclathrate hydrates. The adsorption on these two hydrates was studied by zeta potential and pyrene fluorescence measurements. CP hydrates have a negative surface charge in the absence of SDS, and it decreases to a minimum as the SDS concentration increases from 0 to 0.17 mM. Then, it increases with further increased SDS concentration. The adsorption density of DS- on CP hydrates reaches a saturated value at 1.73 mM SDS. The micropolarity parameter of the TBAB hydrate/water interface starts to increase rapidly at 0.17 mM SDS and levels off at 1.73 mM SDS. The presence of Br- in TBAB hydrate suspensions could compete with TBADS (from association of DS- and TBA(+)) and DS- for the adsorption on the hydrate surface, but they have a much stronger affinity for the hydrates than does Br-. From the fluorescence measurements, it was found that the micropolarity of the hydrate/water interface is mainly dependent on the polarity of hydrate formers.