The invention discloses a mixture of poly-pneumococcal capsular polysaccharide-protein conjugates. The mixture contains 13 pneumococcal capsular polysaccharide-protein conjugates and an immunity-enhancement adjuvant, wherein each pneumococcal capsular polysaccharide-protein conjugate is formed by combining corresponding serum-type pneumococcal capsular polysaccharide with a same protein carrier through a covalent bond; the 13 pneumococcal capsular polysaccharides are obtained by purifying and extracting 1, 3, 4, 5, 6A, 6B, 7F, 9V, 14, 18C, 19A, 19F and 23F bacteria; the protein carrier is A chain of a diphtherin mutant CRM197 obtained from expression of genetic recombinant escherichia coli. Meanwhile, the invention discloses a preparation method of the mixture. The mixture, compared to conventional bacterial fermentation total-chain diphtherin mutant CRM197, is easy to purify, high in yield and low in cost; experiments prove that the mixture disclosed by the invention is immunogenic, and is applicable to clinical inoculation.