Calcium alginate (Ca-Alg) is a novel target product for recovering alginate from aerobic granular sludge. A novel Ca-Alg production method was proposed herein where Ca-Alg was formed in a sodium alginate (SA) feed solution (FS) and concentrated via forward osmosis (FO) with Ca reverse osmosis using a draw solution of CaCl. An abnormal reverse solute diffusion was observed, with the average reverse solute flux (RSF) decreasing with increasing CaCl concentrations, while the average RSF increased with increasing alginate concentrations. The RSF of Ca in FS decreased continuously as the FO progressed, using 1.0 g/L SA as the FS, while it increased initially and later decreased using 2.0 and 3.0 g/L SA as the FS. These results were attributed to the Ca-Alg recovery production (CARP) formed on the FO membrane surface on the feed side, and the percentage of Ca in CARP to total Ca reverse osmosis reached 36.28%. Scanning electron microscopy and energy dispersive spectroscopy also verified CARP existence and its Ca content. The thin film composite FO membrane with a supporting polysulfone electrospinning nanofiber membrane layer showed high water flux and RSF of Ca, which was proposed as a novel FO membrane for Ca-Alg production via the FO process with Ca reverse diffusion. Four mechanisms including molecular sieve role, electrification of colloids, osmotic pressure of ions in CARP, and FO membrane structure were proposed to control the Ca-Alg production. Thus, the results provide further insights into Ca-Alg production via FO along with Ca reverse osmosis.