Coxy
The value returned by the DIO Read vi is going to be an array of 8 bit integers. I'm not sure what you mean by 32 bit chuncks, however, The total number of elements in this array equals the number of ports in the group multiplied by the number of scans to read. For example, if your group contains two ports, then elements 0 and 1 contain the data for the first scan. Both of which are 8 bits.
You are correct in that the 6534 will not allow you to have send an odd number of bytes, it will give you a 10010 error. Therefore, when the amount of data to be transferred has to be even for one port, though does not matter for two or four ports.
Brian