Pueblo is a very family-centric city with a lot of history, so naturally there are a lot of family owned and privately owned businesses. Most of these are restaurants and retail shops - i.e. Solar Roast Coffee, Razmataz, Seabel's, and The Daily Grind. However, there are a lot of chain restaurants and retail stores as well that provide a lot of income for the city's citizens; there are definitely a lot of people who work in these kinds of customer service jobs.
The presence of several hospitals and medical centers (St. Mary Corwin, Parkview Medical Center, Southern Colorado Clinic, etc.) also provides a lot of jobs for Pueblo. This city is also home to the state mental health facility, and I've known several people who were employed there.