This study investigates the negative impact of temperature on spodumene flotation from the perspective of the gas–liquid interface of sodium oleate (NaOL) solutions. Micro-flotation tests revealed a significant decrease in the flotation recovery of spodumene when NaOL was employed as a collector, dropping from 55.3% at 305.4 K to 5.1% at 277.3 K as the temperature decreased. A strong linear correlation between the surface tension of the NaOL solution and temperature was established. As the temperature decreased, the surface tension of 6 × 10⁻⁵ mol/L NaOL increased from 37.88 mN/m at 294.9 K to 40.71 mN/m at 281.9 K, while its critical micelle concentration decreased from 9.49 × 10⁻⁴ mol/L at 305.0 K to 6.85 × 10⁻⁴ mol/L at 288.0 K. Additionally, molecular dynamics (MD) simulations indicated that a decrease in temperature resulted in an enhancement of intermolecular action forces, a more compacted interfacial structure, and weakened molecular thermal motion at the gas–liquid interface of the NaOL solution. These variations were found to be the main reason for the rise in the surface tension of the NaOL solution as the temperature decreased, which in turn lowered its efficiency, resulting in a decrease in the flotation efficiency of spodumene.