The Papa John's Trophy final will be played after a nervy penalty shootout victory.
Millers forward Michael Smith scored two trademark heads to give the Millers a 2-0 lead.
Both sides missed their kicks in the first five spot-kicks to take the game to sudden death.
Mickel Miller won it after Tom Crawford missed for Pools.
The final will be played at Wembley on 3 April.
While form might have favored League One leaders Rotherham, who had lost just once in their past 11 games before this one, they were given a huge scare by a side who have already beaten three other teams.
A full house, a North Sea breeze and a collected approach gave the home side the motivation to take the game to their higher division opponents.
With the wind in their favor, they took control, Grey tucked away a curling David Ferguson free-kick to go in front, and only the goalkeeping prevented them further joy.
In order to turn things around, they brought on attacking talent in Miller and Chiedozie, as well as adding Ollie Rathbone to the mix.
Big forward Smith met crosses from Dan Barlaser and Ogbene to drag the visitors back level, after a superb finish from Molyneux restored the Pools lead.
As the visitors chased a winner in normal time, Killip was inspired by the fact that he beat away a Ogbene finish and that the Vikings keeper made a big save from Molyneux.
Crawford's skied shot was a second miss after Molyneux had already seen his kick saved, and it was Crawford who was left rueing their fortunes.
Miller made no mistake with the deciding kick, prompting celebrations for those in red and white, but for Pools it was so close, so far as the cup dream ends and the crowd is drifting away.
The boss of Hartlepool told the radio station.
You couldn't not enjoy the game. The effort against a top team in League One is immense. They kept going and were effective despite everything we did to stop them.
We created chances, scored goals, and performed well, but we have to take so much from that. We had to dig in at times. I thought we were done when we scored the penalty. I did not look. I was waiting for the fans to respond and I think Ben was close.
The missed penalties were not a problem for me because the lad stepped up to take the penalties, which was something I never did as a player. We have to look at the positives and not dwell on it.
Paul Warne is the boss of Rotherham.
It is pretty amazing. Before the game, I told the players to do it for their families, and for their mother who drove them to training every day for 10 years.
It is a nice way to show your appreciation to the people who love you. When they are older and have children of their own, they will realize how important it is.
If we are going to lose, I told them to give everything. We had to make eight changes. I am really pleased that the subs made an impact.
The conditions had an effect, but our better players imposed themselves in the second half.
Formation 4-3-3.
2Sterry16Byrne5Odusina3Ferguson6Shelton8Featherstone22CrawfordFormation 3-1-4-2.
23Edmonds-Green6Wood21MacDonald7Osei-Tutu16Lindsay22Odoffin15Bola
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