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An innovative bitopic phosphoramidite ligand L was proficiently synthesized and subsequently employed in coordination with two distinct metal species (AgI and RhI), leading to the construction of a heterometallic coordination polymer. The catalyst showcased remarkable performance in the hydroformylation of long-chain alkenes, displaying high activity and selectivity with a minimum yield of 90% for aldehydes. Operating as a heterogeneous catalyst, it not only demonstrated outstanding efficacy in facile separation from the product but also maintained a low rhodium loss per catalytic cycle. The catalyst exhibited exceptional stability, remaining high activity and selectivity over 10 successive reuses. Moreover, the RhAgL catalysts exhibit notable isomerization effects on alkenes, which promote the preferential formation of branched aldehydes in the resulting product. The straightforward synthetic strategy employed in preparing this highly effective catalyst introduced an innovative concept for heterogeneous catalysis, offering promising prospects for advancing industrial processes. This remarkable performance indicates the catalyst's potential for sustainable and efficient chemical transformations, highlighting its significance in driving advancements in catalytic technology for a variety of applications in industry.Graphical Abstract: An innovative bitopic phosphoramidite ligand L was proficiently synthesized and subsequently employed in coordination with two distinct metal species (AgI and RhI), leading to the construction of a heterometallic coordination polymer. The catalyst showcased remarkable performance in the hydroformylation of long-chain alkenes, displaying high activity and selectivity with a minimum yield of 90% for aldehydes. Operating as a heterogeneous catalyst, it not only demonstrated outstanding efficacy in facile separation from the product but also maintained a low rhodium loss per catalytic cycle. The catalyst exhibited exceptional stability, remaining high activity and selectivity over 10 successive reuses. Moreover, the RhAgL catalysts exhibit notable isomerization effects on alkenes, which promote the preferential formation of branched aldehydes in the resulting product. The straightforward synthetic strategy employed in preparing this highly effective catalyst introduced an innovative concept for heterogeneous catalysis, offering promising prospects for advancing industrial processes. This remarkable performance indicates the catalyst's potential for sustainable and efficient chemical transformations, highlighting its significance in driving advancements in catalytic technology for a variety of applications in industry. [ABSTRACT FROM AUTHOR]