Over　the　past　few　decades,　layer-by-layer　(LbL)　assembly　of　multilayer　thin　films　has　garnered　considerable　interest　on　account　of　its　ability　to　modulate　nanometer　control　over　film　thickness　and　its　extensive　choice　of　usable　materials　for　coating　planar　and　particulate　substrates,　thus　allowing　for　the　fabrication　of　responsive　and　functional　thin　films　for　their　potential　applications　in　a　myriad　of　fields.　Herein,　we　provide　elaborate　information　on　the　current　developments　of　LbL　assembly　techniques　including　different　properties,　molecular　interactions,　and　assembly　methods　associated　with　this　promising　bottom-up　strategy.　In　particular,　we　highlight　the　principle　for　rational　design　and　fabrication　of　a　large　variety　of　multilayer　thin　film　systems　including　multi-dimensional　capsules　or　spatially　hierarchical　nanostructures　based　on　the　LbL　assembly　technique.　Moreover,　we　discuss　how　to　judiciously　choose　the　building　block　pairs　when　exerting　the　LbL　assembly　buildup　which　enables　the　engineering　of　multilayer　thin　films　with　tailor-made　physicochemical　properties.　Furthermore,　versatile　applications　of　the　diverse　LbL-assembled　nanomaterials　are　itemized　and　elucidated　in　light　of　specific　technological　fields.　Finally,　we　provide　a　brief　perspective　and　potential　future　challenges　of　the　LbL　assembly　technology.　It　is　anticipated　that　our　current　review　could　provide　a　wealth　of　guided　information　on　the　LbL　assembly　technique　and　furnish　firm　grounds　for　rational　design　of　LbL　assembled　multilayer　assemblies　toward　tangible　applications.