We report a hybrid thin-film deposition procedure to significantly enhance the reflectivity of La/B-based multilayer structures. This is of relevance for applications of multilayer optics at 6.7-nm wavelength and beyond. Such multilayers showed a reflectance of 64.1% at 6.65 nm measured at 1.5-degrees off-normal incidence at PTB (BESSY-II). This was achieved by a special scheme of La passivation. The La layer was nitridated to avoid formation of the optically unfavorable LaBx compound at the B-on-La interface. To avoid the also undesired BN formation at the La-on-B interface, a time-dosed nitridation at the initial stage was applied. This research revealed a good potential for further increase in the reflectivity of multilayer structures at 6.7 nm.