Low-rank coals are difficult to float using common hydrocarbon oily collectors, such as dodecane and diesel. In this investigation, a mixture of dodecane and n-valeraldehyde was used as a collector to enhance low-rank coal flotation. The changes of the contact angle and surface functional groups of low-rank coal were measured before and after different collectors’ adsorption to indicate its absorption mechanism. Surface tension of different collectors was also measured to identify its spreading performance. The results showed that the flotation performance using the mixture as a collector was much better than that using dodecane or n-valeraldehyde solely. When used the mixture of dodecane and n-valeraldehyde as collector, dodecane primarily covers the hydrophobic sites while n-valeraldehyde primarily covered the hydrophilic sites by hydrogen bond promoting adsorption of dodecane at these sites. There existed synergistic effect between dodecane and n-valeraldehyde. Additionally, n-valeraldehyde can reduce the surface tensions to improve the spreading performance of mixed collector on low-rank coal surface. The improvement both in adsorption and spreading was responsible for the enhancement of low-rank coal flotation by using the mixture.