Goodfellow had to wait until the British National Cup in Southend in January 2016 to again compete in 10m diving. He participated in the individual 10m competition and teamed up with Tom Daley in the 10m sychro competition. Goodfellow first met Tom Daley, the 2012 London Olympics individual 10m bronze medalist, in 2015. He won bronze in the individual 10m dive and a gold with Daley in the 10 m synchro.
Goodfellow and Daley earned a place in the 10m platform synchro competition at the 2016 Olympics in Rio de Janeiro by winning the bronze medal at the FINA Diving World Cup on 21 February 2016. They produced the single best synchro 10m diving score, achieving it with a forward four-and-a-half somersault (109C), with a difficulty of 3.7, which was awarded 91.02 points. Goodfellow and Daley won medals at each of the 2016 FINA World Series 10m synchro events – Beijing (bronze), Dubai (silver), Windsor (silver), Kazan (bronze) – and were second place overall. They improved their score each time they competed in the FINA World Series – Beijing (420.15), Dubai (428.91), Windsor (441.84), Kazan (442.59). Goodfellow and Daley were the first Britons to win medals in all the 10m synchro FINA World Series events in one year.
On 12 May 2016 at the European Championships, Goodfellow and Daley earned their seventh consecutive 10m synchro medal. They were in position for gold after the first five dives of the competition, but had to settle for silver after Germany passed them by less than one point in the final round. On 10 June 2016 at the British National Championships Goodfellow and Daley won gold in the 10m synchro. Their Front 4 ½ Somersaults tucked dive (109C) was their best single dive in the competition, and received a score of 95.46.
Goodfellow and Daley earned a bronze medal in the 2016 Olympic 10m synchro competition in Rio on 8 August primarily by scoring 92.13 on their fifth dive, which was a 109C with a 3.7 degree of difficulty. This was their highest scoring dive. This score moved them from fifth to third. Their sixth dive was a 207B dive, with a 3.6-degree of difficulty, and had to be 84 or higher for them to maintain third place and edge out Germany. The score of 89.64 for their sixth dive ended the competition, and resulted in the bronze medal for Goodfellow and Daley.