The American stormed ahead 6-2 in the final set tiebreak before sealing victory on his first match point when Karlovic netted a backhand.
"To say that I felt like I'd be the winner at the end of the week ...I had no idea," doubles specialist Ram told reporters.
"The first (title) win (in Newport) was more elation, this one is more satisfaction just because I did it again. That last tiebreaker was about as good as I can play."
The 31-year-old Ram, who will climb from 161st to 86th when the new world rankings are issued on Monday, also booked a coveted spot at this year's U.S. Open with his triumph.
The opening set went with serve and into a tiebreak before the American went ahead with a mini-break at 5-4 after unleashing a stunning forehand crosscourt winner.
Ram held serve to lead at 6-4 before he pushed a backhand volley wide for 6-5. Karlovic, on serve, netted a volley to lose the set after just under an hour.
A sliced backhand winner down the line by Karlovic in the 11th game of the second set gave him a breakpoint which he converted when Ram hit a forehand volley long. The Croat then held to level the match at one-set all.
The final set also went with serve before Ram took control of the decisive tiebreak by going 5-1 up.
Though the six-foot 11-inch (2.11 metres) Karlovic trimmed the deficit to 5-2, Ram held to lead 6-2 before sealing victory.
Karlovic, seeking a seventh ATP World Tour title, had to settle for a second consecutive runner-up spot in Newport, having lost last year's final in three sets to Australian veteran Lleyton Hewitt.
"In the end, he was a little bit better," said Karlovic, ranked 24th. "Like last year, it was a really tight match. I could have won both years. There's always next year."
(Reporting by Mark Lamport-Stokes in Los Angeles; Editing by Gene Cherry)
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