Sean Astin (Twoflower) and Sir David Jason (Rincewind) are long-term Terry Pratchett fans. Jason named "The Colour of Magic" as his choice of favorite book of all time in the BBC's Big Read survey.
Richard da Costa (Luggage) is also the Librarian as an orangutan. He studied real orangutans in a zoo to learn how they moved.
The colors of the pattern on Twoflower's shirt aren't as garish as the description in the book, but they had to be chosen to avoid primary colors, or they'd have vanished in the bluescreen and greenscreen sequences.
Nigel Planer (Arch Astronomer) was also the narrator of several unabridged Discworld audio books, including the "The Colour of Magic" and "The Light Fantastic" (on which this mini-series was based). He also voiced multiple characters in all three of the Discworld video games.