Wollaston was born in Norfolk, England, and was one of seventeen children in an academically prominent family. His great grandfather, for whom he was named, authored Religion of Nature Delineated, a widely read volume on natural religion. His father, Francis Wollaston, a vicar and member of the British Royal Society, compiled a catalog of stars which was published in 1880.

Wollaston entered Cambridge to pursue the study of languages, but he was drawn by his interest in the sciences to study medicine. In his pursuit of a medical degree, which he earned in 1792, he studied botany and developed an interest in chemistry. This interest was furthered by the opportunity to perform experiments in his brother's laboratory (the elder Wollaston held a lectureship in chemistry). He began his medical practice in 1792 and became a fellow of the Royal Society in 1793. In 1800, citing his deteriorating eyesight, he left his practice to...