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A DOI, or Digital Object Identifier, is a unique identifier given to many articles that are being written. An example of a DOI would be 10.1017/S0022149X13000114.
They are useful, because in some citation styles the DOI will replace other information stating where the article was found. For instance, instead of stating the database, and URL where the article was located, you can place the DOI instead. The reader of an article could then paste the DOI, found in your bibliography, into what is called a DOI resolver. The DOI resolver would recognize the article associated with that DOI and show where it could be accessed.
The DOI can usually be found in the database record for an article, and is often times imported to RefWorks with the other article information. Not all articles will have a DOI.