A Mg/Al layered double hydroxide (LDH) was intercalated with the anionic herbicides 2,4-D, MCPA, and picloram by using three different methodologies: (i) direct synthesis (DS), (ii) regeneration (RE), and (iii) ion exchange (IE). The resulting complexes were characterized and assayed by batch release and column leaching tests, aiming at the controlled release of these herbicides. All the tested LDH-herbicide complexes displayed similar slow herbicide release properties in water, although the IE method seemed to result in complexes with a greater fraction of herbicide in a readily available form. Apparently, the LDH-herbicide complexes released most of the active ingredient present in the complexes at the end of the batch release experiment. This was attributed to the replacement of the intercalated herbicide by carbonate and hydroxyl anions from the aqueous solution. Compared to the free herbicides, the application of the three LDH-herbicide complexes (RE) to soil columns resulted in reduction in the maximum herbicide concentration in leachates and led to the retardation of herbicide leaching through the soil. All LDH-herbicide complexes presented an herbicidal efficacy similar to that of the free (technical) herbicides. Our results indicated the potential applicability of LDHs as supports for the preparation of slow release formulations of acid herbicides such as 2,4-D, MCPA, or picloram.