Great autogenous shrinkage has become a common problem in cement-based materials with a low water-to-binder ratio (w/b). To limit the autogenous shrinkage in ultra-high performance concrete (UHPC) during the process of hydration and curing, sustainable use of recycled micropowder (RMP) made from autoclaved aerated concrete waste (AACW) to cure UHPC internally is proposed in this paper. The influence of RMP (at the levels 5%, 10%, and 15% by mass) with three particle size classes ranging from 0 to 600 μm on the autogenous shrinkage, hydration reaction, internal relative humidity, and compressive strength of UHPC were investigated. The results show that mixtures with different dosages and particle sizes improve the fluidity of UHPC, and its internal curing effect can effectively inhibit the early-age autogenous shrinkage of UHPC and maintain a higher internal humidity compared with the control group. The incorporation of RMP can advance the appearance of a hydration peak and increase the cumulative heat of hydration. Microscale analyses show that the curing water released from RMP promotes the hydration of the unhydrated cement around RMP. The generated hydration product filled the surface pores of RMP and weakened the negative effect of the pores introduced by RMP on the compressive strength of UHPC. Thus, RMP can be utilized as internal curing materials for UHPC to reduce autogenous shrinkage.