The school's director Heinrich Conried recognised his considerable vocal ability and in 1907 sent the young Alfred to Prague, where he studied with Ludmilla Prochazka-Neumann (1872–1954).
His studies led to a three-year contract with the Deutsches Landes-Theater in Prague where he made his debut on 9 September 1907 in Otto Nicolai's The Merry Wives of Windsor.
This variety stood him in good stead, because in 1910, he was invited to appear as a guest in Mattia Battistini's touring company that was performing in Prague.
However, he continued to sing with the Prague company for the remainder of his contract and it was not until 6 September 1912 that he gave his first performance with the Vienna State Opera as a permanent member.
Piccaver had a warm, velvety, lyric tenor voice with a fine cantilena style and excellent legato and diction.
Piccaver loved Vienna and the Viennese way of life, so much so that when the director of the Metropolitan Opera in New York, Giulio Gatti-Casazza, made a lucrative offer for him to appear at the Met, he turned it down.
In 1923, for reasons that are not clear, he claimed British nationality as he was entitled to do as a result of his place of birth, though Alfred Piccaver always considered himself an American.
Piccaver's first marriage was to Baroness Mariette Styrcea (born Marietta Johanny, died 11 Nov 1934), the daughter of an Austrian Lutheran minister.