•Structure-property relation of oxidized sodium alginate (OSA) was investigated.•Molecular weight of OSA is a key factor in improving properties of collagen fiber.•Effect of aldehyde group content was less obvious than that of molecular weight. A series of periodate oxidized sodium alginate (OSA) were prepared as green polysaccharide-based crosslinkers. The molecular weight of OSA decreased, while their aldehyde group content increased with increasing dosage of sodium periodate. A typical OSA was further fractionated to four fractions by ethanol with a narrower molecular weight distribution. Then the crosslinking performances of OSAs/fractions on collagen fiber (CF) were investigated. DSC and SEM analyses showed that the thermal stability and dispersion degree of crosslinked CF was considerably enhanced with decreasing molecular weight of OSA. The effect of aldehyde group content of OSA on its crosslinking performance was less obvious than that of molecular weight, probably because the aldehyde group content in each OSA sample was higher than the amino group content of CF involved in the crosslinking reaction. In general, molecular weight of OSA plays a decisive role in improving properties of the crosslinked CF.