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There are four forms of B12: cyanocobalamin, hydroxocobalamin, adenosylcobalamin, and methylcobalamin. All are available in supplement form, although some are easier to find than others. My understanding is that they are all B12 at different stages of "processing."
Methylcobalamin and cyanocobalamin are almost the same chemical structure, except that cyanocobalamin has a cyano group (CN) bonded to its central cobalt atom, while methylcobalamin has a methyl (CH3) group in its place.
Cyanocobalamin is the more common recommendation because it has been studied more than methylcobalamin. Cyanocobalamin is also more stable, and it's usually cheaper. However, if you're a smoker or have kidney failure, you should avoid cyanocobalamin.
Most people believe that methylcobalamin is superior to cyanocobalamin because it does not require this extra step. And because of the prevalence of genetic methylation defects, pre-methylated forms of B12 are thought to be superior.
Cyanocobalamin is a synthetic form of vitamin B12 found only in supplements, while methylcobalamin is a naturally occurring form that you can get through either food sources or supplements.
Methylcobalamin is a natural form of vitamin B12, and cyanocobalamin is synthetic. The two forms also differ in structure—methylcobalamin contains a methyl group, and cyanocobalamin contains a cyanide compound.
Research on people on a vegan diet has shown that cyanocobalamin and methylcobalamin are both helpful in addressing vitamin B12 deficiency. According to the study, cyanocobalamin was more effective in maintaining healthy levels of serum vitamin B12 (called holotranscobalamin) than methylcobalamin.