Struve, who was born at Altona in Germany, moved to Dorpat in Latvia in 1808 in order to escape conscription into the Napoleonic army then in control of Germany. He took a degree in philology in 1811 before becoming professor of astronomy and mathematics in Dorpat in 1813. In 1817 he became director of the Dorpat Observatory, which he equipped with a 9.5-inch (24-cm) refractor that he used in a massive survey of binary stars from the north celestial pole to 15°S. He measured 3112 binaries – discovering well over 2000 – and cataloged his results in Stellarum Duplicium Mensurae Micrometricae (1837; Micrometric Measurements of Double Stars).

In 1835 Czar Nicholas I persuaded Struve to set up a new observatory at Pulkovo, near St. Petersburg. There in 1840 Struve became, with Friedrich Bessel and Thomas Henderson, one of the first astronomers to detect parallax. He chose Vega, a bright star with a larger-than-normal proper motion and soon established a parallactic measurement (that was, however, too high).

Struve founded a dynasty of astronomers that is still in existence. He was succeeded by his son Otto at Pulkovo, his grandson Hermann became director of the Berlin Observatory, and his great-grandson, Otto Struve, became director of the Yerkes Observatory in Wisconsin.