We describe here the design of a liquid cell specific for synchrotron X-ray reflectometry (XRR) characterisation of soft matter nanofilms at the mica–water interface. The feature of the cell is a “bending mica” method: by slightly bending the mica substrate over an underling cylinder the rigidity of the mica sheet along the bending axis is enhanced, providing sufficient flatness along the apex of the cylinder as required by XRR measurements. Using this cell, we have performed XRR measurements for a number of systems and in this article we show example results: (1) a cationic surfactant, C16TAB; (2) a zwitterionic surfactant, C12H25PC; (3) a semi-fluorinated surfactant, F4H11(d)TAB; and (4) surface complex of an anionic fluorinated surfactant, CsPFN, and a positively charged polymer, PEI. For the data analysis we have taken into account the mica crystal truncation rod, i.e. the reflectivity from the mica substrate, and fitted the data with a custom Java™ based software package. Our results unravel detailed structural information of these soft nanofilms, indicating that this method is suitable for XRR measurements of a wide range of soft matter structures at the mica–water interface.