The goal of this study was to investigate the effect of the structure of Mn-Al layered double hydroxide (LDH) on the adhesion behavior of composite adhesives on two Al alloys (L3005 and L8079). The composite adhesives were made out of the UV-curing Bisphenol A glycidylmethacrylate/triethylene glycol dimethacrylate (BT) as polymer matrix and the addition of 1, 3, and 5 wt. % of Mn-Al LDH as adhesion enhancers. Adhesion was evaluated by using the micro Vickers hardness testing procedure. The wetting angle of composite adhesives to the Al substrates was measured and compared to the adhesion parameter b obtained from the microhardness tests. The highest increase in adhesion was observed for BT with 5 wt. % of Mn-Al LDH on L3005 substrate, which was more than 15 times higher than the adhesion for the neat BT. The morphological segregation of composite adhesives after the contact with Al substrates was examined by optical microscopy and a higher compatibility of Mn-Al LDH particles with L3005 substrate was found. The methods used for the adhesion properties assessment suggested that the Mn-Al LDH was the best adhesion enhancer of the BT matrix for L3005 substrate containing a higher content of Mn and surface hydroxyl groups.