Catassembly is a new concept in molecular assembly that is analogous to catalysis in chemical synthesis. However, for most molecular-assembled processes, the catassembler contributions are rather inconspicuous due to the low activation barriers. As a result, few systems dealing with the catassembly are available until now. In this paper, we report that naphthalene diimide coordination networks are formed under the catassembly of lone-pair-bearing catassemblers(e.g., N,N-dimethylacetamide, N-methylpyrrolidin-2-one). During such molecular assembly, a stable transition state between the electron-deficient naphthalene diimide tectons and catassemblers via the less common lone pair-π interactions was observed, which is supposed to play the key role in the enhancement of coordination abilities of organic tectons and thus formation of the final coordination networks. Catassembly is a new concept in molecular assembly that is analogous to catalysis in chemical synthesis. However, for most molecular-assembled processes, the catassembler contributions are rather inconspicuous due to the low activation barriers. As a result, few systems dealing with the catassembly are available until now. In this paper, we report that naphthalene diimide coordination networks are formed under the catassembly of lone-pair-bearing catassemblers (eg, N, N-dimethylacetamide, N-methylpyrrolidin- a stable transition state between the electron-deficient naphthalene diimide tectons and catassemblers by the less common lone pair-π interactions was observed, which is supposed to play the key role in the enhancement of coordination abilities of organic tectons and thus formation of the final coordination networks.