Precise　synthesis　of　high-quality,　sophisticated　heterostructures　by　ordered　assembly　of　small　nanomaterials　is　a　key　step　to　gain　advanced　materials　that　have　elaborate　functionalities,　collective　properties,　and　enhanced　stabilities　for　mitigating　the　energy　and　environment　crisis.　Intricating　in　the　structure,　size,　and　shape　of　nanomaterials,　ordered　assembly　of　isotropic　or　anisotropic　nanoscale　building　blocks　to　create　specified　heterostructures　remains　challenging,　owing　to　the　extraordinary　challenges　in　design　of　lattice　topology　of　distinct　nanounits　and　in　control　of　their　crystallization,　growth,　and　assembly　mechanism/kinetics.　Herein,　the　emerging　methodologies　to　prepare　a　diversity　of　ordered　heterostructures　with　strengthened　particle–particle　interaction　are　examined　and　synergistic　properties　are　enhanced.　It　is　aimed　to　unlock　the　principles　to　regulate　the　geometrical　and　electronic　properties　of　these　intriguing　kinds　of　heterostructures　for　respective　sustainable　energy　and　environmental　applications.　Current　challenges　and　opportunities　in　customization　of　ordered　heterostructure　at　the　nanoscale　and　atomic　level　are　also　discussed.　©　2023　The　Authors.　Advanced　Energy　and　Sustainability　Research　published　by　Wiley-VCH　GmbH.