The flocculation of small surficial groups on pristine CNCs (carbon nanocoils) bundles limit their application. In this study, we designed and fabricated novel array CNCs with a surficial decoration of polyaniline (PANI) using in situ methods. Atomic layer deposition (ALD) and chemical vapor deposition (CVD) methods were employed to fabricate the highly pure array CNCs. The array CNCs decorated with ultra-thin PANI were confirmed by different characterizations. Furthermore, this material displayed a good performance in its detection of formaldehyde. The detection results showed that the CNCs coated with PANI had a low limit of detection of HCHO, as low as 500 ppb, and the sensor also showed good selectivity for other interfering gases, as well as good repeatability over many tests. Furthermore, after increasing the PANI loading on the surface of the CNCs, their detection performance exhibited a typical volcanic curve, and the value of the enthalpy was extracted by using the temperature-varying micro-gravimetric method during the process of detection of the formaldehyde molecules on the CNCs. The use of array CNCs with surficial decoration offers a novel method for the application of CNCs and could be extended to other applications, such as catalysts and energy conversion.