The Metropolis algorithm and the classical Heisenberg approximation were implemented by the Monte Carlo method to design a computational approach to the magnetization and resistivity of La2/3Ca1/3MnO3, which depends on the Mn ion vacancies as the external magnetic field increases. This compound is ferromagnetic, and it exhibits the colossal magnetoresistance (CMR) effect. The monolayer was built with L×L×d dimensions, and it had L=30umc (units of magnetic cells) for its dimension in the x–y plane and was d=12umc in thickness. The Hamiltonian that was used contains interactions between first neighbors, the magnetocrystalline anisotropy effect and the external applied magnetic field response. The system that was considered contains mixed-valence bonds: Mn3+eg’–O–Mn3+eg, Mn3+eg–O–Mn4+d3 and Mn3+eg’–O–Mn4+d3. The vacancies were placed randomly in the sample, replacing any type of Mn ion. The main result shows that without vacancies, the transitions TC (Curie temperature) and TMI (metal–insulator temperature) are similar, whereas with the increase in the vacancy percentage, TMI presented lower values than TC. This situation is caused by the competition between the external magnetic field, the vacancy percentage and the magnetocrystalline anisotropy, which favors the magnetoresistive effect at temperatures below TMI. Resistivity loops were also observed, which shows a direct correlation with the hysteresis loops of magnetization at temperatures below TC.