I never worked for Valero, but did interview there and have heard some additional "third party" info.
Back a few years ago, they were paying low 80K to start in the two LR-60s and two CE-750s. As I recall, there was nothing like a set schedule, but the trips were known in advance. You were expected to show up when not flying to work on projects and I got the impression that guys were just standing around trying to look busy.
My overall impression was that it was an "newly evolving" flight department with rather deep pockets (go figure!). Everyone seemed nice, but they all seemed to be trying to fit into their own corporate mold. A friend described them as "The Stepford Pilots". I think that fits, at least with what I saw.
One other thought...Valero is well known for it's generosity toward charities, especially United Way. That's great, but I believe that they compel their employees to donate. A friend who worked there in a non-flying capacity told me that when he went in to fill out his HR paperwork, they didn't ask if he wanted to donate, they asked how much he wanted to donate, then they said "You can give a little more than that, can't you?" It seems a bit insincere to spend your employee's paycheck for them just so you can have the local paper print a story about how "Valero Employees give X Dollars To Charity". I'd think more of them if they said "We only pay 60K, but your paycheck is going to say 80K because your gonna donate 20K on our behalf, capisce?"
That being said, I'd have taken the job, if offered...I just don't think that I'd have liked it very much.