The leader of the Catholic Church was traveling down a street in Iquique, Chile, after celebrating Mass when the mount reared up.
Cheers for Francis instantly turned to screams as the convoy turned its attention to the condition of the policewoman.
The holy figure stood with the fallen officer until an ambulance arrived that took her away.
The Vatican stated that the officer did not pass out after being flung and that Francis offered “words of consolation” for her.
After making sure the policewoman was in a stable condition, the motorcade then resumed its journey in the Chilean city.
Earlier in the day, the Pope made history after performing a wedding ceremony for two flight attendants on a plane mid-flight from Iquique to the country’s capital, Santiago.
Paula Podest Ruiz, 39, and Carlos Ciuffardi Elorriga, 41, had tied the knot earlier in a civil service but asked for the holy man’s blessing on their marriage.
The pair stated that they were unable to have the occasion in their Santiago church as it was damaged by an earthquake in 2010.
The devastating quake had a magnitude of 8.8 and also triggered a tsunami – the disaster killed at least 500 people.
Francis asked: “Do you want me to marry you?”
The couple replied: “Well, yes, but are you sure?”
A short wedding service then proceeded in the aircraft – a handwritten document was handed to the couple by a travelling cardinal.
The document was then posted on Twitter – it was signed by the couple and Ignacio Cueto, the president of LATAM airlines that acted as a witness.
Greg Burke, a spokesman for the Vatican, said: “Everything is valid. Everything is official.”