Axially, epitaxially organizing nano-objects of distinct compositions and structures into superlattice nanowires enables full utilization of sunlight, readily engineered band structures, and tunable geometric parameters to fit carrier transport, thus holding great promise for optoelectronics and solar-to-fuel conversion. To maximize their efficiency, the general and high-precision synthesis of colloidal axial superlattice nanowires (ASLNWs) with programmable compositions and structures is the prerequisite; however, it remains challenging. Here, we report an axial encoding methodology toward the ASLNW library with precise control over their compositions, dimensions, crystal phases, interfaces, and periodicity. Using a predesigned, editable nanoparticle framework that offers the synthetic selectivity, we are able to chemically decouple adjacent sub-objects in ASLNWs and thus craft them in a controlled approach, yielding a library of distinct ASLNWs. We integrate therein plasmonic, metallic, or near-infrared-active chalcogenides, which hold great potential in solar energy conversion. Such synthetic capability enables a performance boost in target applications, as we report order-of-magnitude enhanced photocatalytic hydrogen production rates using optimized ASLNWs compared to corresponding solo objects. Furthermore, it is expected that such unique superlattice nanowires could bring out new phenomena.