The temperature accelerated dielectric breakdown strength of on-wafer low-k dielectric polymer films with thicknesses ranging from 94 nm to 1141 nm is investigated by using the current-voltage characteristic measurements with MIS structures. The temperature dependence of dielectric strength is demonstrated to be Arrhenious for all thicknesses. However, the activation energy is found to be strongly thickness dependent. It follows an exponential relationship rather than being a single value, i.e., the activation energy increase significantly as film thickness increases for the thickness below 500 nm, but it is almost constant for the thickness above 500 nm. This relationship suggests that the change of the activation energy corresponding to different film thickness is closely related to the temperature dependence of the electron trapping/detrapping process in polymer thin films, and is determined by both the trapping rate and the detrapping rate. Thinner films need less energy to form a conduction path compared to thicker films. Hence, it leads to smaller activation energy in thinner films, and the activation energy increases with the increase in film thickness. However, a nearly constant value of the activation energy is achieved above a certain range of film thickness, indicating that the trapping rate and detrapping rate is almost equal and eventually the activation energy approaches the value of bulk material.