When the couple of five years exchanged personal vows in a romantic Italian ceremony Oct. 19, "it was a really special evening," Timberlake, 31, tells PEOPLE in this week's cover story, in which the newlyweds open up for the first time about their special day and share exclusive photos.
"It was a total fantasy experience," adds Biel, 30.
One cause for emotion? The singer-actor played the guitar and serenaded his beautiful bride-to-be as she walked down the aisle in a custom, petal pink Giambattista Valli Haute Couture gown.
"It was an original piece I wrote specifically for the evening and for her," says Timberlake, who wore a Tom Ford tux he helped design.
The pair welcomed 100 guests, including close friends Jimmy Fallon, Andy Samberg, Timbaland and Biel's 7th Heaven costar Beverley Mitchell, to the Borgo Egnazia resort in southern Italy for a week-long wedding celebration.
"It was a lot to ask of them to travel, so we figured we'd give our guests a good party!" says Timberlake.