Beta-TCP (β-TCP) particle-containing LA/PCL micro/nanofibers were fabricated via a one-step electrospinning process. The morphology and chemical structure of the composite nanofibers were characterized by FESEM, XRD, and FTIR. Rougher surfaces were observed for the LA/PCL micro/nanofibers containing β-TCP compared to the neat LA/PCL fibers, which could possibly provide extra sites for cell binding. XRD and FTIR confirmed the presence of β-TCP as being firmly deposited on the fibers. After an immersion in distilled water, we observed that the β-TCP-containing composite fibers were more degradable with many damaged and broken fibers compared to the LA/PCL fibers. MTT assay and immersion test showed better cell viability and proliferation, and improved mineralization ability compared to the LA/PCL only mat. Thus, the incorporation of β-TCP and the presence of LA in PCL micro/nanofibers could result to an improved biocompatibility and faster degradation of the composite fibers, which would possibly be useful for tissue scaffold application.