He was the Superintendent of the London Fire Brigade from 1861 to 1891, where he introduced modern firefighting methods and increased the number of stations. He is noted for his adoption of the famous brass helmets. Among his other accomplishments, Shaw expanded the use of steam fire engines and also introduced the use of the telegraph for communication between stations. He was an influential thinker on firefighting, publishing at least one book on the subject. However, Shaw is perhaps now best remembered for being mentioned in one of the Gilbert and Sullivan operettas. At the premiere of Iolanthe, he was escorted to a front-row seat and became immortalized in Gilbert and Sullivan lore when the Fairy Queen opened her arms to him and sang:
Oh, Captain Shaw!
Type of true love kept under!
Could thy Brigade with cold cascade
Quench my great love, I wonder!
Whereas Shaw blushed profusely, he had the good grace to stand up at the conclusion of the piece and take a bow.