Paula Podest Ruiz, 39, and Carlos Ciuffardi Elorriga, 41, had been married earlier in a civil service but asked the Pope to bless their marriage. "Here?" they replied, to which the pope responded "yes" and promptly married the happy couple.
The lucky couple was supposed to have their wedding in 2010.
Pope Francis on Thursday performed another first, a wedding ceremony for a steward and stewardess, aboard a plane taking him between two Chilean cities.
He then carried out a Catholic wedding service for the couple, lining up the airline's boss as a witness.
According to Ciuffardi, Francis told them what happened "was historic", because "never has a Pope married a couple on a plane".
In what has garnered lots of applaud for the Pontiff, Pope Francis on Thursday stopped his motorcade and came down from his auto - the Pope mobile - to attend to a policewoman who was thrown off her horse, in Iquique, Chile.
"When people make a mistake it's necessary that they ask for forgiveness", said Monica Reyes, a nursing assistant who attended the pope's speech at the presidential palace.
"There is no Christian joy when doors are closed; there is no Christian joy when others are made to feel unwanted, when there is no room for them in our midst", he said in the homily of Mass on a beach in this city in Chile's far north.
Francis asked them if they were married and the couple told him they had been scheduled to be Wednesday when the 2010 Chile natural disaster hit, destroying the church where they were to tie the knot.
In a trip that has been less than positive for Pope Francis, there was a bit of a shock.
Referring to the rings, Francis jested that they shouldn't be too tight, because "they would be a torture", nor too loose, because they might lose them.
"What he said to us is very important: "This is the sacrament the world needs, the sacrament of marriage. Marriage works...we hope it will promote marriage".
"I asked him: 'Do you marry people?' He said: 'Yes, from time to time".