The simplest form of carbohydrates are monosaccharides which are the building blocks for the synthesis of polymers or complex carbohydrates. Monosaccharide contents of 197 rice accessions were quantified by HPAEC‐PAD in rice (Oryza sativa L.) whole grain (RWG). A genome‐wide association study (GWAS) was carried out using 33,812 single nucleotide polymorphisms (SNPs) to identify corresponding genomic regions influencing neutral monosaccharides contents. In total, 49 GWAS signals contained in 17 genomic regions (quantitative trait loci [QTLs]) on seven chromosomes of rice were determined to be associated with monosaccharides contents of whole grain. The QTLs were found for fucose (1), mannose (1), xylose (2), arabinose (2), galactose (4), and rhamnose (7) contents, all of which are novel. Based on co‐location of annotated rice genes in the vicinity of GWAS signals, the constituents of the whole grain were associated with the following candidate genes: arabinose content with α‐N‐arabinofuranosidase, pectinesterase inhibitor, and glucosamine‐fructose‐6‐phosphate aminotransferase 1; xylose content with ZOS1‐10 (a C2H2 zinc finger transcription factor [TF]); mannose content with aldose 1‐epimerase‐like protein and a MYB family TF; galactose content with a GT8 family member (galacturonosyltransferase‐like 3), a GRAS family TF, and a GH16 family member (xyloglucan endotransglucosylase/hydrolase xyloglucan 23); fucose content with gibberellin 20 oxidase and a lysine‐rich arabinogalactan protein 19, and finally rhamnose content with myo‐inositol‐1‐phosphate synthase, UDP‐arabinopyranose mutase, and COBRA‐like protein precursor. The results of this study should improve our understanding of the genetic basis of the factors that might be involved in the biosynthesis, regulation, and turnover of monosaccharides in RWG, aiming to enhance the nutritional value of rice grain and impact the related industries.