Watching from the sidelines at both men and women's ice skating events, the royal couple were clearly enjoying themselves as they soaked up the vibrant atmosphere.
Willem-Alexander, 46, and Máxima, 42, jumped up in unison to applaud the Dutch athletes competing in the races and looked thrilled when the Netherlands scooped three medals for the men's speed skating on the first day.
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Ever the stylish royal, Máxima looked elegant in a navy blazer and trousers ensemble paired with a crisp white shirt. The mother-of-three brightened up her outfit with an orange scarf, proudly sporting the Netherlands' national colour, while Willem-Alexander matched his wife in an orange waterproof jacket.
The couple, who are parents to three girls Catharina-Amalia, Alexia and Ariane, looked loved-up as they shared a tender moment from the side and affectionately gazed at each other.
The reigning monarchs were joined by the Dutch prime minister Mark Rutte and IOC member and CEO of Dutch airline KLM Camiel Eurlings. The group looked to be enjoying each other's company, as they were pictured laughing at something on Máxima's phone.
Earlier in the day, Willem-Alexander and Máxima were spotted cycling together on orange bicycles around the Olympic village, where they picked up some souvenirs.
This is not the first time the Dutch royals have stepped out in support of their country at a major sporting event. During the London Olympics in summer 2012, Willem-Alexander and Máxima brought their children along to cheer on the Netherlands.
The family-of-five were pictured on the edge of their seats during one women's swimming relay and spurred the athletes on to silver. In recognition of Máxima's display of passion, the swimmers threw her their bouquet from the podium.