The 19-year-old was second in the standings after coming home in a time of 1:10.582, but ended up sixth in a high-quality competition that saw China's Li Zhangyu smash the world record to claim gold.
Rolfe already has a bronze to his name from the C2 3000m individual pursuit on Friday, and he is expecting to further add to his medal tally as part of the team sprint on Sunday.
"It's a multi-classification event, so I knew coming into it that it would be hard to get a good result, so I'm really happy with where I've come," he said.
"It was just a mixture of emotions [watching the other athletes race]. I wanted my time to stand but at the same time, I could see that they were doing better times than me. I've just got to be happy with how I went.
"I think having such a good start that I did yesterday really carried me well through for the next couple of days. Tomorrow is the team sprint and we're world champions in that event so I'm expecting a high positioning, but we'll have to see what we can do on the day."