stability, biodegradability, ease of functionalization, and compromised toxicity. [1,2] Notably, polysaccharide/inorganic nanohybrids are considered ideal candidates as multifunctional platforms to combine the virtues of polysaccharides and intriguing inorganic nanoparticles. [3] Favorable synergistic properties arising from their integration could also be anticipated. [4] Recently, a variety of polysaccharide/inorganic nanohybrids have been fabricated via a nonsolvent-aided counterion complexation method while the morphology was limited to symmetrical spheres. [5-8] It is still a great challenge to obtain a controlled synthesis of a series of polysaccharide/ inorganic nanohybrids with adjustable morphologies to integrate the advantages of both components. On the other hand, unsymmetrical nanoparticles, especially Janus nanoparticles (JNPs), have attracted widespread interest since the morphology of nanoparticles greatly influences their properties and interactions with biological systems. [4,9,10] Compared with symmetrical core-shell-structured hybrid nanoparticles, JNPs demonstrate improved magnetic, optical, and drug-loading properties with more exposed areas of the components to maintain their characteristics. [11-13] Moreover, Near-infrared (NIR) light-responsive JNPs are also found to realize enhanced photothermal effect and penetration in tumors through self-propulsion, which is driven by the temperature gradient across the Janus boundary. [14-16] In these examples, photothermal gold nanoparticles including gold shells and stars were usually employed as a component of JNPs to realize active motion under NIR irradiation. On the other hand, gold nanorods are intriguing due to their tunable optical properties with different aspect ratios, which could be utilized to optimize photothermal performance and selective release of DNA by laser irradiation at different wavelengths. [17,18] However, distinct gold nanorods responsive to specific wavelengths of NIR light are still not well exploited in the fabrication of JNPs with enhanced photothermal performance. Gene therapy is considered a promising therapeutic modality to complement the limited light penetration of photothermal The unsymmetrical morphology and unique properties of Janus nanoparticles (JNPs) provide superior performances for biomedical applications. In this work, a general and facile strategy is developed to construct a series of symmetrical and unsymmetrical chitosan/gold nanoparticles. Taking advantage of the active motion derived from Janus structure, selective surface functionalization of polysaccharide domain, and photothermal effect of gold nanorods, Janus chitosan/gold nanoparticles (J-Au-CS) are selected as a model system to construct Janus-structured chitosan/gold nanohybrids (J-ACP). Near-infrared (NIR)-responsive J-ACP composed of polycationic chitosan nanospheres and PEGylated gold nanorods hold great potential to realize photoacoustic (PA) imaging-guided complementary photothermal therapy (PTT)/gene therapy for breast cancer. The morphol...