{| class="wikitable" style="text-align:right"
|+Napoleonville racial composition as of 2020
!scope="col"| Race
!scope="col"| Number
!scope="col"| Percentage
|-
!scope="row"| White (non-Hispanic)
| 84
| 15.56%
|-
!scope="row"| Black or African American (non-Hispanic)
| 428
| 79.26%
|-
!scope="row"| Native American
| 1
| 0.19%
|-
!scope="row"| Other/Mixed
| 12
| 2.22%
|-
!scope="row"| Hispanic or Latino
| 15
| 2.78%
|}
As of the 2020 United States census, there were 540 people, 229 households, and 137 families residing in the village.
Notable people
<!--Notable people with Wikipedia articles, in alphabetical order-->
- Troy E. Brown, former member of the Louisiana State Senate and native of Napoleonville
- Paul Carmouche, former district attorney for Caddo Parish
- Papa Celestin, jazz bandleader
- Philip H. Gilbert, politician, former lieutenant governor
- Joe Harrison, state representative
- Brandon Jacobs, retired NFL running back
- Samuel A. LeBlanc I, state representative, state court judge, justice of the Louisiana Supreme Court from 1949 to 1954
- Charlie Melançon, former U.S. representative
- Jordan Mills, NFL offensive lineman
- J.C. Politz, sportscaster
- Tramon Williams, NFL cornerback
- Kim Willoughby, Team USA Volleyball (2008 Beijing Olympics)
National Guard
The village is home to the 928th Sapper Company, a combat engineer unit of the 769th Engineer Battalion of the Louisiana Army National Guard which in turn is headquartered at Baton Rouge. Both of these units belong to the 225th Engineer Brigade headquartered at Louisiana National Guard Training Center Pineville near Pineville.
Twin towns
The town maintains twinning links with:
Pontivy (Napoléonville in 1804), France since 1989