Prior to 1885, the publishers of the DNB created a set of approximately 28,000 named individuals whose biographies were to be included in the DNB. These were alphabetized and divided into 63 sets. The editors then produced a volume for each set, in alphabetical order. They produced volumes at three-month intervals, starting at the beginning of 1885 and ending in 1900.

Each article was written by an individual contributor. With the exception if a few "anonymous" articles, each article terminates with the initials of the contributor.

Each volume starts with a list of contributors. The list gives the contributor's name and the initials That are used to attribute an article to that contributor. Each volume then continues with the actual biographical articles. Each volume concludes with a volume table of contents.