Abstract Silver bismuth disulfide (AgBiS 2 ) colloidal nanocrystals (CNCs) have emerged as ecofriendly photoactive materials with excellent photoconductivity and high absorption coefficients, in compliance with the restriction of hazardous substances (RoHS) guidelines. To maximize the theoretical potential of AgBiS 2 CNC solar cells, a new diketopyrrolopyrrole (DPP)‐based polymer, BD2FCT, optimized as a hole transport layer (HTL), is developed. This asymmetric thiophene‐rich polymer HTL effectively complements the optical absorption spectrum of CNCs and forms a homogeneous layer atop the CNCs, facilitating favorable vertical charge transfer through intrinsic molecular packing. Furthermore, the BD2FCT HTL aligns energetically with AgBiS 2 , significantly reducing charge recombination at the CNC/HTL interfaces and enhancing charge extraction and photocurrent generation across the entire optical absorption spectrum. These characteristics are further optimized through precise molecular engineering. Additionally, a low‐bandgap acceptor, IEICO‐4F, is structurally incorporated with the BD2FCT polymer to further improve charge funneling and complementary absorption. Transient absorption spectroscopy reveals enhanced hole transfer from CNC to BD2FCT‐29DPP:IEICO‐4F, resulting in reduced charge recombination and efficient charge extraction. Consequently, a BD2FCT‐based AgBiS 2 CNC solar cell achieves a power conversion efficiency (PCE) of 10.1%, demonstrating significant improvements in short‐circuit current density ( J SC ) and fill factor ( FF ).

When we touch an object, thermosensation allows us to perceive not only the temperature but also wetness and types of materials with different thermophysical properties (i.e., thermal conductivity and heat capacity) of objects. Emulation of such sensory abilities is important in robots, wearables, and haptic interfaces, but it is challenging because they are not directly perceptible sensations but rather learned abilities via sensory experiences. Emulating the thermosensation of human skin, we introduce an artificial thermosensation based on an intelligent thermo-/calorimeter (TCM) that can objectively differentiate types of contact materials and solvents with different thermophysical properties. We demonstrate a TCM based on pyroresistive composites with ultrahigh sensitivity (11.2% °C–1) and high accuracy (<0.1 °C) by precisely controlling the melt-induced volume expansion of a semicrystalline polymer, as well as the negative temperature coefficient of reduced graphene oxide. In addition, the ultrathin TCM with coplanar electrode design shows deformation-insensitive temperature sensing, facilitating wearable skin temperature monitoring with accuracy higher than a commercial thermometer. Moreover, the TCM with a high pyroresistivity can objectively differentiate types of contact materials and solvents with different thermophysical properties. In a proof-of-principle application, our intelligent TCM, coupled with a machine-learning algorithm, enables objective evaluation of the thermal attributes (coolness and wetness) of skincare products.