The composition and structure of kerosene co-refining products (KCR) need to be studied to promote their further processing and utilization besides for making fuels. In this paper, their composition and structure were analyzed layer by layer from top to bottom in the form of “Surface (KCR)-Line (six group components, SGCs)-Point (compounds)”. SGCs combine extraction and column chromatography to provide a method for highly efficient separation of heavy hydrocarbons. Insoluble components (asphaltene, ASP) and n-heptane soluble (HS) were obtained from light and heavy liquids (LP and HP) of KCR by Soxhlet extraction. HS was gradient eluted by chromatographic column with different solvents and α-Al2O3, and separated into other five group components: saturates (SA), aromatics (AR), heteroatoms (HE), phenolics (PH) and resins (RE), wherein the results show that the extraction yields of LP-SA, LP-AR, LP-PH, LP-RE are 68.53 wt%, 7.28 wt%, 3.55 wt% and 1.20 wt%, and the extraction yields of HP-SA, HP-AR, HP-HE, HP-PH, HP-RE are 36.06 wt%, 25.13 wt%, 6.27 wt%, 4.53 wt% and 2.37 wt%, respectively. Physical and chemical characterization of the raw materials and SGCs were analyzed by TG, FTIR, 13C NMR, GC/MS, and Py-GC/MS, in which the combination of GC/MS and Py-GC/MS can fully detect the light and heavy components in LP and HP, including those difficult to detect above 300 °C. The final thermal mass loss rates of these components follow the order of LP-SA > LP-AR > LP-PH > LP-RE and HP-SA > HP-AR > HP-PH > HP-HE > ASP > HP-RE. The aromatic carbon mass ratio (fa) of LP and HP is 15.27% and 19.45%, respectively. n-Alkanes (C11–32) are the main compounds in LP and HP, followed by polycyclic aromatics with 3–4 R. Aromatics are rich in -CH2- bridge bond to generate light aliphatics and aromatics at 500 °C, especially the ASP generates many monocyclic aromatics with the increase of temperature by Py-GC/MS. In addition to aliphatics and aromatics, alkyl phenols, esters, pyridines and thiophenes are the main compounds in LP and HP.