I did something similar to this a year or two back, going through all of Trek chronologically with TNG/DS9, DS9/VOY episodes interpersed (though no B5) and had a great time. I did make some preferential tweaks here and there, such as swapping around "Past Prologue" and "A Man Alone" as the later was produced first and works better a second episode. Tried to tackle Voyager in production order as much as possible also, such as watching season 1 episodes ("Twisted", "Projections", etc) that were held back til season 2 in their "proper" place.
Currently watching Buffy and Angel for the first time and doing the same thing. Crossovers there are even better than they were on Trek. Watching "Fool for Love" and "Darla" back to back was an absolute blast!