In the recent past, the use of inter-electrode slit (IES) in modified electrochemical machining (MECM) has shown promising results in terms of improved material removal rate (MRR), surface roughness (Ra), and controlled dimensional deviation (Δd). But hitherto little has been reported on the comparison of morphological characteristics (porosity (P)%, grain size No., Ra, etc.) and dimensional stability features (Δd and aspect ratio (AR)) for its acceptance as a tool room process. This study outlines the morphological and dimensional characteristics of MECM (at pre-fixed settings: IES of 6 × 6 mm2 cross section, thickness 3 mm, voltage, feed rate, electrolyte concentration, etc.) with the use of Cu alloy as tool material and Cu/Al/ Ti alloy as workpiece (W/P) for possible applications in aerospace, electronic circuit boards, and automobiles. The results outlined that the highest Ra value (27.48 µm) was observed for Al W/P in line with the observed material removal rate (MRR) as 7.5 × 10−5 cm3/s, and dissolution rate (DR) as 2.08 × 10−6 cm/s. The study suggests that from Δd, and P% viewpoint the best W/P material is Ti (with Δd: 1.27, and P: 1.93%) followed by Al (Δd: 1.98, and P: 3.79%) and Cu alloy (Δd: 5.73, and P: 65.46%). The results have been supported by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Ra, P%, and grain size number.