Known as Alphonse, he was the eldest son of James Mayer de Rothschild (1792-1868). His mother was Betty de Rothschild (1805-1886), the daughter of Salomon Mayer von Rothschild from the Austrian branch of the family. Alphonse was educated to take his place at the head of de Rothschild Frères bank, training in the other Rothschild banking houses in Europe. In France he soon became a major force in the financial world and in 1855 was appointed a regent of the Banque de France, a position he held for the remainder of his life.
In 1857 Alphonse de Rothschild married a cousin, Leonora "Laure" de Rothschild (1837-1911), the daughter of Lionel de Rothschild (1808-1879) of the English branch of the family. They had the following children:
On the death of their father in 1868, Alphonse and Gustave inherited the Château Lafite-Rothschild vineyard. However, they lived in Paris and the vineyard was not significant relative to their massive investments in banking and other business ventures. As such, they only visited the Pauillac vineyard occasionally, maintaining little more than an arms-length interest. On their deaths, the Rothschild brothers willed the property to a son and it remains in family hands to this day.
During the 1860s, great debates raged across Europe and the United States as to an appropriate monetary system for the changing times. In France, the prominent Péreire brothers bankers were proponents of paper money in contrast to Alphonse de Rothschild who defended preservation of France's bimetallism system. Initially, Alphonse had an influential supporter for his position through his long friendship with statesman Léon Say, a former employee of the Rothschild's Northern Railway Company who became the Minister of Finance in 1872. However, as part of the Latin Monetary Union France joined most of the rest of Europe and adopted the gold standard by 1873. In 1880, Alphonse de Rothschild put together the deal that saw the family take control of Société Le Nickel (SLN), a nickel mining business in New Caledonia.
During the Franco-Prussian War, Alphonse de Rothschild had guarded the ramparts of Paris on the eve of the Prussian siege. When a peace treaty was finally agreed to in January of 1871, his bank would play a major role, not only in raising the five billion francs France was obliged to pay in reparations to the new German Empire, but in helping bring about economic stability. France made a dramatic financial recovery and repaid the reparations bill ahead of schedule which, under terms of the armistice, brought about an end to the German occupation of northern French territory in 1873. In contrast though, that same year, both the Berlin and Vienna stock markets crashed, plunging all of Central Europe into an economic depression. However, in less than a decade Alphonse de Rothschild would witness considerable economic upheaval in France. The collapse of the investment bank Société de l'Union Générale precipitated the 1882 stock market crash that triggered a downturn in the economy. In 1889, the Comptoir d'Escompte de Paris bank went into receivership and shortly thereafter the Panama scandals erupted, culminating in an official enquiry being conducted into the matter in 1893 by the French parliament.
Already made a member of the Legion of Honor, for his contributions to the French economy at a time of crisis, in 1896 Alphonse de Rothschild was elevated to the Grand Cross, the highest class of the Legion of Honor.
On his passing in 1905, Alphonse's son Edouard took over as head of the family business.