We derive new characterisations of the matrix $\mathrmΦ$-entropy functionals introduced in [Electron.~J.~Probab., 19(20): 1--30, 2014]. Notably, all known equivalent characterisations of the classical $Φ$-entropies have their matrix correspondences. Next, we propose an operator-valued generalisation of the matrix $Φ$-entropy functionals, and prove their subadditivity under Löwner partial ordering. Our results demonstrate that the subadditivity of operator-valued $Φ$-entropies is equivalent to the convexity of various related functions. This result can be used to demonstrate an interesting result in quantum information theory: the matrix $Φ$-entropy of a quantum ensemble is monotone under unital quantum channels. Finally, we derive the operator Efron-Stein inequality to bound the operator-valued variance of a random matrix.