To enhance the application of nanobubbles in the field of flotation, it is crucial to comprehend the synergistic effects between nanobubbles and collectors. Atomic force microscopy studies revealed nanobubble formation on the calcite surface, with the size of the bubbles increasing as vacuum pressure decreased. The addition of sodium oleate surfactant resulted in an increase in the number and size of nanobubbles. Zeta potential and particle size measurements demonstrated that the zeta potential of nanobubbles was negative and decreased upon the addition of sodium oleate. Furthermore, sodium oleate reduced the size of the nanobubbles and stabilized them. Particle size measurements and high-speed camera analysis of calcite flocs indicated that nanobubbles alone cannot significantly increase the flocculation size of −10 μm calcite, but when combined with sodium oleate, they can increase flocculation size based on the presence of sodium oleate. The adhesion between calcite particles, generated from the hydrophobic attraction of nanobubbles, was unstable and could be easily disrupted by external forces. Surfactants played a crucial role in the stability of the flocs. Nanobubble-assisted flocculation has been shown to enhance the flotation recovery of calcite.