H-MFI type zeolitic materials of different Si/Al ratios have been completely or partially cesium-exchanged (cesium content ranging from 0.7 to 7.7 Cs/unit-cell (uc)). Examined with synchrotron X-ray powder diffractometry, an anhydrous sample with the Cs6.6H0.3Al6.9Si89.1O192 chemical composition revealed at ambient temperature the presence of five discrete Cs locations: Cs1 located in the channel intersection near a 10-ring window of the zigzag channel; Cs2 and Cs2', both located in the straight channel but 1.23 A apart; Cs3 and Cs3', both located in the zigzag channel and rather close to each other (2.51 A). The populations of the Cs species amounted to 2.61/0.81/1.85/0.86/0.47/uc for Cs1/2/2'/3/3', respectively. The continuous but multimodal nature of the C2 split site is well-described by a joint-probability density function. The 10-ring of the straight channel in the framework is highly elliptical (epsilon = 1.218). The populations for the same sites were also determined at higher temperatures: 131, 237, 344, and 450 degrees C. At 450 degrees C, Cs2' has migrated toward the center of the channel intersection, and the site separation between Cs2 and Cs2' has lengthened to 2.23 A. Using a temperature-controlled laboratory X-ray diffractometer, similar studies were carried out on partially or almost totally Cs-exchanged samples from various sources with differing Cs contents. They show that over the 0.7 to 4 Cs/uc range all the individual Cs populations vary linearly as a function of total Cs/uc present. At higher total Cs/uc content (4 to approximately 7 Cs/uc) solely Cs1 continues to do so. For Cs2+Cs2' and Cs3+Cs3', the variation is almost linear over the whole concentration range. Computer simulations using a 6-exp-1 Buckingham-type atom-atom van der Waals interaction model yield six possible Cs sites in the actual Cs6.6MFI framework structure. Four of them lie very close to those determined from difference Fourier maps using the room temperature data. A fifth one is close to the Cs2' species after thermal migration at 450 degrees C, and the sixth one is close to the center of the channel intersection. However, this latter site is observed experimentally only in the case of hydrated CsMFI phases. In the anhydrous Cs6.6MFI phase at room temperature, the shortest Cs-framework oxygen distance is Cs3'-O25 = 3.08 A, and the next shortest distances are Cs1-O26 = 3.37, Cs2-O11 = 3.34, Cs2'-O22 = 3.47, and Cs3-O20 = 3.34 A. The framework T(Si,Al) sites most involved in these contacts are the T9, T11, T12, T10, and T3 sites. This implies that these sites are prime candidates for Si/Al substitution.