Accurate division of heterotic group in maize can provide effective information on germplasm improvement, heterosis mode construction, and development of new varieties. The main methods used at present to divide maize heterotic group are pedigree, combining ability test, isozyme markers, and molecular markers. These methods are inferior because of their high cost and operational complexity. Some of them even have to destroy the seeds. This study explored novel method feasibility of near infrared (NIR) spectroscopy in quick nondestructive heterotic grouping of maize. The near infrared diffuse reflection spectra of maize seeds were collected and preprocessed using smoothing, first derivative, and vector normalization. The features of these spectra were extracted through principal component analysis (PCA). Twelve Chinese maize inbred line samples were selected, including six leading inbred lines (Part A) and six excellent self-selection lines (Part B). Part A was divided into three groups with NIR spectroscopy, namely, A1 (Zheng58) and A2 (Ye478), A3 (Chang7-2) and A4 (Huangzaosi), and A5 (Mo17) and A6 (SiF1). This division was in accordance with pedigree analysis. Part B was also divided into three groups by NIR spectroscopy: B1 and B2, B3 and B4, as well as B5 and B6. This division conforms to clustering analysis based on SSR molecular marker. These processes confirm that NIR spectroscopy is a convenient, highly efficient, and feasible heterotic grouping method of maize.