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After helping Francisco Pizarro conquer the Incas, Sebastián de Belalcázar quarreled with his former boss and moved north to strike out on his own. After founding Quito and Popayán, he arrived in the Valle del Cauca in 1536, where he dubbed his new settlement Santiago de Cali. At the time of his arrival, the fertile valley was inhabited by various indigenous groups, of which the Calima community was the most advanced.

They initially offered stiff resistance to the Spanish presence, though in the long run the real impediment to growth was Cali's proximity to Popayán, which was the political and economic center of the region until the end of the 19th century. That said, much of Popayán's wealth actually came from the sugar plantations in the region around Cali. To work the fields, the Spaniards shipped in thousands of African slaves over the centuries, and the African legacy is still very much in evidence today; a significant portion of the population is of African or mixed African and European descent.

It was the arrival of the railroad at the beginning of the 20th century that sealed Cali's fate. Suddenly cash crops could reach world markets, and the newly rich sugar and coffee barons, needing to reinvest their earnings, built a thriving industrial base. This in turn led to explosive economic growth, especially after the 1940s.

Today, Cali is the capital of Valle del Cauca and is home to half of the department's population. As well as being the third-largest city after Bogotá and Medellín, it's the dominant industrial, agricultural and commercial center of the southwest.