The influence of a carbon barrier layer to improve the reflectivity of Cr/Ti multilayers, intended to be used in the water window wavelength regime, is investigated. Specular grazing-incidence X-ray reflectivity results of Cr/Ti multilayers with 10 bilayers show that interface widths are reduced to ~0.24 nm upon introduction of a ~0.3 nm C barrier layer at each Cr-on-Ti interface. As the number of bilayers increases to 75, a multilayer with C barrier layers maintains almost the same interface widths with no cumulative increase in interface imperfections. Using such interface-engineered Cr/C/Ti multilayers, a remarkably high soft X-ray reflectivity of ~31.6% is achieved at a wavelength of 2.77 nm and at a grazing angle of incidence of 16.2°, which is the highest reflectivity reported so far in the literature in this wavelength regime. Further investigation of the multilayers by diffused grazing-incidence X-ray reflectivity and grazing-incidence extended X-ray absorption fine-structure measurements using synchrotron radiation suggests that the improvement in interface microstructure can be attributed to significant suppression of inter-diffusion at Cr/Ti interfaces by the introduction of C barrier layers and also due to the smoothing effect of the C layer promoting two-dimensional growth of the multilayer.