We report the synthesis of a family of ferrimagnetic NiFe layered double hydroxides (LDHs) with a variable Ni(2+)/Fe(3+) in-plane composition of [Ni1-xFex(OH)2](CO3)x/2·yH2O (x = 0.20, 0.25, and 0.33) by following a modified homogeneous precipitation. These layered magnets display high crystallinity, homogeneous hexagonal morphologies, and micrometric size that enable their quantitative exfoliation into single layers by sonomechanical treatment of the solids in polar solvents. This was confirmed by dynamic light scattering, UV-vis spectroscopy, high-resolution transmission electron miscroscopy, and atomic force microscopy methodologies to study the resulting steady suspensions. Our magnetic study reflects that the iron content in the LDH layers controls the overall magnetism of these lamellae. Hence, the gradual replacement of Ni(2+) with Fe(3+) centers introduces a larger amount of antiferromagnetically coupled Fe-OH-Fe pairs across the layers, provoking that the compound with the highest Fe/Ni ratio displays spontaneous magnetization at higher temperatures (Tirr = 15.1 K) and the hardest coercive field (3.6 kG). Mössbauer spectroscopy confirms that the cation distribution in the layers is not random and reflects the occurrence of Fe clustering due to the higher affinity of Fe(3+) ions to accommodate other homometallic centers in their surroundings. In our opinion, this clarifies the origin of the glassy behavior, also reported for other magnetic LDHs, and points out spin frustration as the most likely cause.