Continuous real-time measurement of body temperature using a wearable sensor is an essential part of human health monitoring. Electrospun aligned carbon nanofiber (ACNF) films are employed to assemble flexible temperature sensors. The temperature sensor prepared at a low carbonization temperature of 650 degrees C yields an outstanding sensitivity of 1.52% degrees C-1, high accuracy, good linearity, fast response time and excellent long-term durability. Moreover, it exhibits high discriminability towards temperature amidst other unwanted stimuli and maintains its original performance even after repeated stretch/release cycles because of highly-aligned structures. The correlation between the atomic structure and the temperature sensing performance of ACNF sensors is established. Contrary to conventional highly conductive temperature sensors, the ACNF sensor with a low electrical conductivity prepared at a low carbonization temperature ameliorates the temperature sensing performance. This anomaly is explained by (i) the smaller and more disordered sp(2) carbon crystallites yielding a high negative temperature coefficient, (ii) a larger number of defects, and (iii) a higher pyridinic-N content generating abundant entrapped and localized electrons which are activated once sufficient thermal energy is available. Flexible ACNF sensor's overall performance is among the best-known carbon material-based flexible temperature sensors, demonstrating potential applications in emerging healthcare and flexible electronics technologies.