In 1808 Marchand went to Spain where he fought in the Peninsular War. In Ney's absence, he took command of the corps and suffered a humiliating defeat at Tamamés at the hands of a Spanish army. He went with Marshal André Masséna's abortive invasion of Portugal in 1810 and 1811 and fought at Ciudad Rodrigo, Almeida, and Bussaco. During the retreat he performed well in one rear guard action against the British and later led his division at Fuentes de Onoro.