Toluca's nightlife is more about cafes than clubs — the altitude is high, the evenings cool, and locals drink coffee or atole under the Portales until late. The cafes under the arcades on the main plaza are the obvious meeting point; Café Casa Toluca and Cafetería Italiana both do reliable coffee with a slice of pastry.
For drinks, a handful of bars cluster on the streets behind the cathedral. La Vaquería Distrito is a respectable craft-beer place. The hotel bars on the western end of town are reliable for a quiet drink. Avoid the larger, more anonymous discos out toward the highway unless you have a local guide.