According to the density functional theory (DFT) calculations, the first hyperpolarizabilities of the carbon nanocone (CNC)–based systems in a D–π–A framework can be prominently improved by constructing the mixed π-conjugated bridge. The hybrid π-conjugated bridge is constructed by modifying the bottom edge of CNC with –(CH CH) x –NH 2 /NO 2 chain. By connecting the –(CH CH) x –NH 2 chain with electron-donating characteristic, the first hyperpolarizabilities of these cone-chain systems can be enhanced more availably, and the substitution position can also play an important role in determining the β 0 value. The TDDFT calculations show that building the simple cone-chain motif can effectively improve the degree of charge transfer and reduce the transition energy, thus leading to a considerably large first hyperpolarizability, which is much larger than that of the corresponding directly NH 2 -decorated CNC system with the same conjugated length. Especially, the first hyperpolarizabilities of these cone-chain motifs (CNC–(CH CH) x –NH 2 ) can increase dramatically with the extension of –(CH CH) x –NH 2 chain. Furthermore, in view of the unique horn-shaped structure of CNC, another –(CH CH) x –NH 2 chain is added at the bottom edge for double-substitution, and it can further augment the first hyperpolarizability compared with the single-substitution. In addition, the length ratio of cone to chain in the mixed π-conjugate bridge can also have a crucial effect on the β 0 value of these cone-chain motifs. Using the –(CH CH) x –NH 2 with a comparable conjugated size to modify the bottom edge of cone can be an effective strategy for achieving the remarkable NLO response in the CNC-based system with D–π–A framework. These fascinating findings are advantageous for the design of new high-performance NLO materials based on CNCs. Constructing a simple cone–chain motif can be considered as a new and effective strategy to significantly increase the first hyperpolarizability of carbon nanocones (CNCs), which can be mainly attributed to the fact that when linking the π-conjugated –(CH CH) x –NH 2 /NO 2 chain with electron-donating/withdrawing characteristic, the abundant π electrons of CNCs can be well directed to result in the more effective charge transfer, just like inserting a straw into a glass of water, it allows the water to flow out more directionally. • Constructing a simple cone–chain motif can significantly increase the first hyperpolarizability of carbon nanocones (CNCs). • The β 0 value of CNC can be enhanced more effectively by linking electron-donating -CH=CH–NH 2 chain. • When elongating the chain length, a monotonous increasing trend can be observed for the β 0 value. • The double-chain substitution of –(CH=CH) x –NH 2 can further enhance the β 0 value of CNC system. • The β 0 value of CNC l –(CH=CH) x –NH 2 can be adjusted effectively by changing the length ratio of cone to chain.