Transfer behaviors of molded polytetrafluoroethylene (PTFE) blocks embedded in metal substrates were studied using a DFPM reciprocating tribometer under designed conditions. The substrate properties markedly affected the embedded PTFE transfer behaviors. For instance, the surface friction coefficient when embedded in AISI-1045 steel had evident fluctuations even after 1000 cycles although the friction coefficient decreased with the increase of the sliding cycles. On the other hand, the friction coefficient when the PTFE was embedded in 2024Al was remarkably reduced during the first 200 cycles, reaching a low and stable state. The loads played different roles in the transfer process; a higher load was advantageous for the steel-PTFE embedded composites, but it resulted in the opposite result for the Al-PTFE embedded composites. The motion direction of the GCr15 tribometer steel ball had no remarkable effect on the transfer behaviors. The worn surface of the substrates and the steel ball were observed and analyzed using scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS). The results indicate that the efficiency of second transfer film formation on the 2024Al substrate was better than for the AISI-1045 steel. The adhesion properties of Al enhanced the mechanical transfer of PTFE during the friction process.