An experimental study, supported by computation, was conducted on the coupling of NTC-chemistry and transport in the low-temperature ignition and the associated steady burning in nonpremixed DME/air counterflow. In particular, the presence of low-temperature chemical reactivity was detected nonintrusively by using a photomultiplier tube combined with a filter to capture the chemiluminescence of HCHO, which is a characteristic intermediate species formed in low-temperature chemistry. Furthermore, the ignition temperature was determined through high-sensitivity infrared imaging with proper discrimination of the background signal. Experimental results show that the transport-coupled low-temperature, NTC chemical reactivity is enhanced with smaller strain rate, higher air boundary temperature, and is insensitive to the fuel concentration. These findings agree well with those obtained from computation using detailed chemistry, leading to further identification of the controlling chemistry. (C) 2014 The Combustion Institute. Published by Elsevier Inc. All rights reserved.