Does anyone know how I can store large binary values in Riak?
Use either the Erlang interface ( http://hg.basho.com/riak/src/461421125af9/doc/basic-client.txt ) or the "raw" HTTP interface ( http://hg.basho.com/riak/src/tip/doc/raw-http-howto.txt ). It should "just work."
Also, you'll generally find a better response on the riak-users mailing list than you will here. http://lists.basho.com/mailman/listinfo/riak-users_lists.basho.com (No offense to z8000, who seems to also have answers.)
For now, they don't recommend storing files larger than 50MB in size without splitting them. See: FAQ - Riak Wiki
If your files are smaller than 50MB, than proceed as you would with storing non binary data in Riak.
Another reason one might pick Riak is for flexibility in modeling your data. Riak will store any data you tell it to in a content-agnostic way — it does not enforce tables, columns, or referential integrity. This means you can store binary files right alongside more programmer-transparent formats like JSON or XML. Using Riak as a sort of “document database” (semi-structured, mostly de-normalized data) and “attachment storage” will have different needs than the key/value-style scheme — namely, the need for efficient online-queries, conflict resolution, increased internal semantics, and robust expressions of relationships.Schema Design in Riak - Introduction