Nano-volcanic ash has been found to be able to improve the performance of asphalt mixtures. This paper selects typical types of volcanic ash which have significant variation in inner pore structure and particle size for comparison. Two sets of experiment have been carried out with some modification to the standard test procedures. The first one is through dynamic rotation shear testing on mastics, with typical volcanic ash fillers and general mineral filler, in full temperature range to approach the mechanism of the interaction between asphalt binder and volcanic ash particles. The second set is based on the results of mastic tests, further discussing the validity of volcanic ash fillers in HMA and evaluating the low and high temperature performance respectively by three points bending test and complex modulus test. Based on lab test results, volcanic ash fillers with the addition of SBS can improve both high and low temperature performance of HMA. The mechanism of action of volcanic ash on HMA has also been discussed. Besides, the test results not only show the improvements on modulus, but also strength and ultimate strain, which influence the low temperature cracking resistance more directly. Some new tests and evaluation methods have been presented