AbstractThe homogeneously catalyzed methoxycarbonylation of methyl 10‐undecenoate allows for the synthesis of dimethyl 1,12‐dodecandioate as an interesting bio‐based drop‐in alternative for 1,12‐dodecandioic acid as polymer building block. Although the benchmark catalyst system of Pd/1,2‐bis((di‐tert‐butylphosphino)methyl)benzene and methane sulfonic acid is very active and selective, long‐term stability over a potential catalyst recycling is limited. In this work, modifications of this catalyst system in terms of protonation of the ligand and its replenishment during recycling are first investigated, proving that the reaction system is tolerant against minor changes. Finally, the commercially available ligand Xantphos, featuring higher stability but comes with a rather low l:b selectivity of 70:30, is applied. However, through the application of cooling crystallization, 58 g product (52% isolated yield) with an overall purity of 94% is obtained from the crude reaction solution without further treatment and a ∑TON of 4000 after ten reaction runs, while catalyst loss into the product is low.Practical Applications: Selective syntheses on the basis of renewable resources are a powerful tool for the production of value products in terms of green chemistry. Thereby, homogeneous transition metal catalysts are beneficial regarding selectivity. However, their separation and recycling are challenging due to their limited stability. The combination of a stable, commercially available catalyst with a selective purification method allows for isolation and purification from a crude reaction mixture without the need for any auxiliary or further purification steps. In this work, cooling crystallization is applied for subsequent purification of the linear diester dimethyl 1,12‐dodecandioate. Thereby, a lower selectivity from the methoxycarbonylation reaction using the stable Xantphos ligand is compensated and combined with recycling of the homogeneous catalyst. Thus, the development of an integrated process covering a stable catalyst system in the reaction, and high selectivity in the purification is the key toward an efficient homogeneous catalyst recycling.