Using more efficient collector to improve the recovery efficiency of fine copper oxide has become imperative as the shortage of copper mineral resources. In this study, the new collector 3-hydroxy butyrate-carboxy methyl cellulose xanthate (HCMCX) was synthesized by carboxy methyl cellulose, 3-hydroxy butyrate and carbon disulfide, all of which as raw materials . The structural characteristics of HCMCX was detected by both infrared spectrum and ultraviolet spectrum. Besides, the interacting behavior between HCMCX and fine malachite was investigated through particle size analysis, contact angle measurements, and flotation tests. Particle size analysis indicated that the mean size of malachite was increased by 8 μm while the HCMCX concentration at 200 mg/dm3. The contact angle measurements demonstrated that, comparing with the collector AX at a same dosage, the mineral surface of malachite showed a stronger hydrophobicity after interacting with HCMCX. Microflotation tests results exhibited that the recovery of malachite was about 94% when the pulp pH 8 and collector concentration at 200 mg/dm3. The results of practical ore flotation tests showed that HCMCX could as an excellent collector for flotation of fine malachite, finally to achieve the concentrates containing 20% Cu and 88% Cu recovery.