About 25 years ago, Bogdanovic and Schwickardi (B. Bogdanovic, M. Schwickardi: J. Alloys Compd. 1-9, 253 (1997) discovered the catalyzed release of hydrogen from NaAlH4. This discovery stimulated a vast research effort on light hydrides as hydrogen storage materials, in particular boron hydrogen compounds. Mg(BH4)2, with a hydrogen content of 14.9 wt %, has been extensively studied, and recent results shed new light on intermediate species formed during dehydrogenation. The chemistry of B3H8-, which is an important intermediate between BH4- and B12H122-, is presented in detail. The discovery of high ionic conductivity in the high-temperature phases of LiBH4 and Na2B12H12 opened a new research direction. The high chemical and electrochemical stability of closo-hydroborates has stimulated new research for their applications in batteries. Very recently, an all-solid-state 4 V Na battery prototype using a Na4(CB11H12)2(B12H12) solid electrolyte has been demonstrated. In this review, we present the current knowledge of possible reaction pathways involved in the successive hydrogen release reactions from BH4- to B12H122-, and a discussion of relevant necessary properties for high-ionic-conduction materials.