He has been the artistic director at Pirelli HangarBicocca since 2012. From 1988 to 1996 he was the artistic director at IVAM (Instituto Valenciano de Arte Moderno), and from 1996 to 2003 he was the director of the Fundaçao de Serralves in Porto. In 2003 he was appointed director of the Tate Modern in London, where he stayed until 2010. Todolí was part of the curatorial team for the 1997 Venice Biennale (directed by Germano Celant) and he has curated individual exhibitions by Miroslaw Balka, Fischli & Weiss, Lucio Fontana, Robert Frank, Hamish Fulton, Joao Maria Gusmao & Pedro Paiva, Richard Hamilton, Gary Hill, Carsten Höller, Roni Horn, James Lee Byars, Cildo Meireles, Mario Merz, Juan Munoz, Damián Ortega, Sigmar Polke, Dieter and Björn Roth, Kishio Suga, Franz West and many more.
Todolí has been a member of the advisory committees and boards at numerous institutions, including the Museo Nacional Centro de Arte Reina Sofía (Madrid), the Amsterdamse Culturele Instellingen (Amsterdam), Carnegie International (Pittsburgh) and Manifesta International Art Foundation (Rotterdam). He was also an artistic consultant at Bombas Gens (Valencia). He is currently a board member at the Fundación Botín (Santander) and a consultant for both the Fundaçao de Serralves (Porto) and the Colección Inelcom (Madrid).