Woolley was born in Exeter and began playing the French horn at age ten having previously played the cornet.[1] Her early teachers include Sue Dent and Simon Rayner. She studied at the Royal College of Music, London and graduated with a first class degree and was awarded the Tagore Gold Medal from the Prince of Wales.[2] While still a student, she was appointed the Third Horn position with the Philharmonia Orchestra and also appeared with them as a soloist.[2] She was the principal horn of the European Union Youth Orchestra for two years. She also studied with Christian-Friedrich Dallman at the Universität der KünsteinBerlin.[2]
At the age of twenty-two Woolley was appointed Principal Horn of the Philharmonia Orchestra.[3] She played with the orchestra for seven years before taking a break to focus on a solo career and teaching. Having previously worked with them as an extra player, in 2019 she was appointed the Principal Horn of the Royal Concertgebouw Orchestra in Amsterdam.[4][5] Woolley plays a hand-hammered Alexander 103.[6]