We study the magnetocaloric effect and the critical behavior of a periodic Anderson-like organic polymer using Green's function theory, in which the localized f orbitals hybridize with the conduction orbitals at even sites. The field-induced metal-insulator transitions with the magnetic Grüneisen parameter showing |Γh|∼T(-1) power-law critical behaviour are revealed, which provides a new thermodynamic means for probing quantum phase transitions. It is found that the competition of up-spin and down-spin hole excitations is responsible for the double peak structure of magnetic entropy change (-ΔS) for the dominant Kondo coupling case, implying a double magnetic cooling process via demagnetization, which follows a power law dependence of the magnetic field h: -ΔS∼h(n). The local exponent n tends to 1 and 2 below and above TC, while has a minimum of 0.648 at TC, which is in accordance with the experimental observation of perovskite manganites Pr0.55Sr0.45MnO3 and Nd0.55Sr0.45MnO3 (J. Y. Fan et al., Appl. Phys. Lett., 2011, 98, 072508; Europhys. Lett., 2015, 112, 17005) corresponding to the conventional ferromagnets within the mean field theory -ΔS∼h(2/3). At TC, the -ΔS∼h curves with a convex curvature superpose each other for small V values, which are separated by the large V case, distinguishing the RKKY interaction and Kondo coupling explicitly. Furthermore, the critical scaling law n(TC) = 1 + (β- 1)/(β + γ) = 1 + 1/δ(1 - 1/β) is related to the critical exponents (β, γ, and δ) extracted from the Arrott-Noakes equation of state and the Kouvel-Fisher method, which fulfill the Widom scaling relation δ = 1 + γβ(-1), indicating the self-consistency and reliability of the obtained results. In addition, based on the scaling hypothesis through checking the scaling analysis of magnetization, the M-T-h curves collapse into two independent universal branches below and above TC.