Fly ash and diatomite were mixed uniformly and ground within various time scale and fly ash/diatomite admixtures with variable particle sizes were obtained. Effects of particle size distributions of the admixtures on the mechanical properties and porosity of concrete were studied. The relationship between the size distribution of the admixture and the concrete porosity was obtained based on the regression analysis of the data. The results show that compressive and flexural strengths of the concrete at 3 d and 7 d increase with the decrease of the admixture particle size. With regards to the concrete at 14 d, lowering the particle size of fly ash/diatomite admixture leads to the increasing of the compressive and flexural strength of the concrete, before decreasing afterwards again. At the d50 value of 15.2 μm, the mechanical properties of concrete were greatly improved. In addition, finer particle of the fly ash/diatomite admixture leads to significant micro-aggregate effect and volcanic ash effect and thus obtains denser pore structure, smaller porosity and higher hydration degree of the cementitious material. Especially for the samples curing at the early stage, the improving effect on the pore structure was obvious.