A few books help make sense of Sucre and the Andean world it sits within.
Marching Powder by Rusty Young is the famous insider's account of life inside La Paz's San Pedro prison — much of the early backstory plays out across Bolivia, including Sucre and Potosí, and there is no better introduction to the chaotic informality of Bolivian institutions. Strange, often funny, occasionally horrifying.
Las venas abiertas de América Latina (Open Veins of Latin America) by Eduardo Galeano is the great polemic on five centuries of resource extraction from the continent. Sucre and especially nearby Potosí are central to the story — the colonial silver that paid for Spain's wars and built Sucre's churches came at the cost of millions of indigenous lives, and Galeano makes you feel it.
Juana Azurduy: La virreina del Alto Perú by Pacho O'Donnell tells the story of Sucre's great indigenous-mestiza war heroine, who fought as a guerrilla through fifteen years of independence campaigns and died forgotten in the city. A good companion to a visit to her birthplace museum.
The Last Frontier by Mike Tidwell is a lyrical first-person account of working with the Bolivian rural development service in Chuquisaca in the late 1980s. It captures the rhythms of the countryside that day-trippers from Sucre see only briefly.
Cumbres borrascosas en los Andes by Néstor Taboada Terán is the most readable contemporary Bolivian novelist on Andean themes — magical realism with a sharper political edge than the Colombians.