Lithium-sulfur (Li-S) batteries have received enormous interest as a promising energy storage system to compete against limited, non-renewable, energy sources due to their high energy density, sustainability, and low cost. Among the main challenges of this technology, researchers are concentrating on reducing the well-known “shuttle effect” that generates the loss and corrosion of the active material during cycling. To tackle this issue, metal-organic frameworks (MOF) are considered excellent sulfur host materials to be part of the cathode in Li-S batteries, showing efficient confinement of undesirable polysulfides. In this study, MIL-88A, based on iron fumarate, was synthesised by a simple and fast ultrasonic-assisted probe method. Techniques such as X-ray diffraction (XRD), Raman spectroscopy, Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), and N2 adsorption/desorption isotherms were used to characterise structural, morphological, and textural properties. The synthesis process led to MIL-88A particles with a central prismatic portion and pyramidal terminal portions, which exhibited a dual micro-mesoporous MOF system. The composite MIL-88A@S was prepared, by a typical melt-diffusion method at 155 °C, as a cathodic material for Li-S cells. MIL-88A@S electrodes were tested under several rates, exhibiting stable specific capacity values above 400 mAh g−1 at 0.1 C (1C = 1675 mA g−1). This polyhedral and porous MIL-88A was found to be an effective cathode material for long cycling in Li-S cells, retaining a reversible capacity above 300 mAh g−1 at 0.5 C for more than 1000 cycles, and exhibiting excellent coulombic efficiency.