The canton Guémené-Penfao has 19 communes.
| Code | Name | Population ▼ |
|---|---|---|
| 44067 | Guémené-Penfao | 5 243 |
| 44113 | Nozay | 4 292 |
| 44149 | Saffré | 4 115 |
| 44051 | Derval | 3 601 |
| 44214 | Vay | 2 120 |
| 44001 | Abbaretz | 2 073 |
| 44224 | La Grigonnais | 1 828 |
| 44197 | Sion-les-Mines | 1 658 |
| 44221 | La Chevallerais | 1 569 |
| 44193 | Saint-Vincent-des-Landes | 1 525 |
| 44091 | Marsac-sur-Don | 1 524 |
| 44076 | Jans | 1 364 |
| 44138 | Puceul | 1 142 |
| 44086 | Lusanger | 1 074 |
| 44044 | Conquereuil | 1 061 |
| 44123 | Pierric | 1 010 |
| 44208 | Treffieux | 996 |
| 44092 | Massérac | 665 |
| 44105 | Mouais | 352 |