He was born in Olten, and studied science and history at the University of Bern, then later took courses in Oriental studies at Munich University and the Sorbonne. He was the son of Josef Munzinger, member of the Swiss Federal Council. In 1852 Munzinger arrived at Cairo, where he spent a year improving his Arabic. Entering a French mercantile house, he led a trading expedition to various parts of the Red Sea. Until 1855 he served as French consul at Massawa, when he moved to Keren where he spent the next six years exploring the lands of the Bogos. In 1861 Munzinger joined Theodor von Heuglin in an attempt to explore central Africa, but separated from him in November, proceeding along the Gash and Atbara to Khartoum. There he succeeded von Heuglin as leader of the expedition, and travelled in 1862 to Kordofan, but failed to reach Darfur and Wadai. After a short stay in Europe in 1863, Munzinger returned to the north and north-east borderlands of Ethiopia. In 1865 Munzinger managed the British consulate along the border of Ethiopia, but remained in Massawa, after the 1868 British invasion of Ethiopia, where he became the French consul. There, according to Augustus B. Wylde, he married a woman of Hamasien and convinced one of the local warlords, Wolde Mikael, to cede the province of Hamasien to France. Munzinger sailed to France, and by early 1870 had an expedition ready at Toulon to sail to Massawa when the Franco-Prussian Warbroke out, and French resources were diverted to this higher priority, whereupon he left the service of the French. In July of that year he was sent to Aden, where he joined Captain S.B. Miles on an expedition into the interior of the southern Arabian peninsula. He then left the French and entered the service of the Egyptian government of Khedive Ismail, serving as governor of the Keren region and Massawa. Once he reached his command, his first act was to place the Bogos once again under Egyptian rule. In 1875, Munzinger led one of the three prongs of the Egyptian attack against Ethiopia, marching inland from Tadjoura, but his troops were overwhelmed by the army of Mahammad ibn Hanfadhe, Sultan of Aussa, and he was killed in battle. Wylde includes in the list of dead Munzinger's wife and child.
He wrote numerous geographical papers, and a memoir on the northern highlands of modern-day Ethiopia and Eritrea for the Zeitschrift für allgemeine Erdkunde, new series, volume 3.