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Abstract We present Atacama Large Millimeter/submillimeter Array Band 3 data toward five massive young stellar objects (MYSOs), and investigate relationships between unsaturated carbon-chain species and saturated complex organic molecules (COMs). An HC 5 N ( J = 35–34) line has been detected from three MYSOs, where nitrogen (N)-bearing COMs (CH 2 CHCN and CH 3 CH 2 CN) have been detected. The HC 5 N spatial distributions show compact features and match with a methanol (CH 3 OH) line with an upper-state energy around 300 K, which should trace hot cores. The hot regions are more extended around the MYSOs where N-bearing COMs and HC 5 N have been detected compared to two MYSOs without these molecular lines, while there are no clear differences in the bolometric luminosity and temperature. We run chemical simulations of hot-core models with a warm-up stage, and compare with the observational results. The observed abundances of HC 5 N and COMs show good agreements with the model at the hot-core stage with temperatures above 160 K. These results indicate that carbon-chain chemistry around the MYSOs cannot be reproduced by warm carbon-chain chemistry, and a new type of carbon-chain chemistry occurs in hot regions around MYSOs.